Process NMR


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2nd Annual Practical Applications of NMR in Industry Conference (PANIC) Announced

Conference Details: 2nd Annual Practical Applications of NMR in Industry Conference
Organized by Cambridge Healthtech Institute
Hilton Charlotte University Place, Charlotte, NC, February 3-5, 2014

Building on the success of last years 1st Annual PANIC NMR Conference it has been decided that the 2nd Annual PANIC NMR Conference would be organized cooperatively between the original organizing committee and CHI.

Details on the conference can be found at: PANIC Conference Website

A promotional flyer for the conference can be found here: PANIC NMR Flyer

Anyone interested in industrial applications of all forms of NMR spectroscopy is encouraged to attend this practical NMR conference where the emphasis is placed on everyday utilization of the technology rather than cutting edge NMR research which is often far beyond the capabilities of the everyday user.

John Edwards of Process NMR Associates is serving on the organizing committee and chairing two technical sessions – one on On-Line/At-Line/Benchtop NMR and another on NMR of Materials.

If you are interested in presenting or sponsoring the conference please contact CHI through the website.

 

 

Process NMR Associates and Pfizer Present Joint Poster on Reaction Monitoring at PittCon

Pfizer has included the Aspect-60 MHz NMR system in their reaction monitoring investigations. The analysis was performed on reactions that were monitored in parallel by a Bruker 400 MHz NMR system. The poster of the initial results will be presented by Dr David Foley of Pfizer at this weeks PittCon in Philadelphia.

The presentation is available here.

SMASH Posters Cover Aloe Vera NMR Test Method, Heavy Petroleum Average Molecule Characterization, and 60 MHz Permanent Magnet NMR Applications

Quantitative 1H qNMR Method for Complex Mixture Analysis: Determination of Acetylated Polysaccharides, Glucose, Maltodextrin, Isocitrate, Preservatives, Additives and Degradation Products in Aloe Vera Leaf Juice – Raw Material and Consumer Products

Practical Applications of Compact, Cryogen-Free High-Resolution 60 MHz Permanent Magnet NMR Systems for Reaction Monitoring and Online/At-Line Process Control

Calculation of Average Molecular Descriptions of Heavy Petroleum Hydrocarbons by Combined Analysis by Quantitative 13C and DEPT-45 NMR Experiments

Process NMR Associates to Contribute Invited Talk and 3 Posters at the 1st Practical Applications of NMR in Industry Conference (PANIC), October 15-17, Schaumburg IL

News – Dr. John Edwards of Process NMR Associates will be presenting the following 3 posters and invited talk at the 1st Practical Applications of NMR in Industry Conference (PANIC), Schaumburg, IL, October 15-17, 2012

Invited Talk

On-line Applications of 60 MHz High-Resolution NMR Systems in Industry: Direct Measurements, Chemometric Correlations, and Multiple Spectroscopy Data Fusion

John C. Edwards Process NMR Associates, LLC, Danbury, CT

For the past two decades high resolution 1H NMR systems combined with chemometric analyses have been utilized in refineries and chemical plants to predict the chemical and physical properties of process streams and finished products. The ability to perform these analyses with on-line NMR instrumentation has allowed tighter control and optimization of the plant to obtain margin improvement, reduced reworking of off-specification materials, and higher yields of finished products. Examples of refinery and petrochemical applications will be given along with some examples of multinuclear NMR applications utilizing 31P and 19F NMR. The permanent magnet based 1.5 Tesla NMR instruments will be described along with a description of how these compact, cryogen-free NMR systems can be utilized on the bench-top or in the fume-hood as continuous or stop-flow chemistry sensors for reaction monitoring, mixing/dilution monitoring, or purity/conversion monitoring. Food applications will also be described such as dairy (butter, cream cheese) and edible or essential oil analysis. Finally, the ability to improve the quality of the correlations derived in the chemometric modelling by “fusing” NMR data with spectral information from other spectroscopies (NIR, Mid-IR) will be discussed.

Poster 1

1H qNMR Determination of Acetylated Polysaccharides, Glucose, Maltodextrin, Isocitrate, Degradation Products, Preservatives and Additives in Aloe Vera Leaf Juice

John C. Edwards Process NMR Associates, LLC, Danbury, CT

Aloe Vera is a botanical component that is used widely in the cosmetic, natural product, herbal supplement, and pharmaceutical industries. The widespread use of Aloe Vera has lead to the need to adequately analyze the authenticity, quality, and quantity of the various components present in this material. The 1H qNMR method described here was developed and validated by Process NMR Associates for a number of NMR service customers and the method will be included in an upcoming Monograph on Aloe Vera published by the American Herbal Pharmacopoeia. The method can be used for the detection and quantitation of the primary components of interest in Aloe Vera juice products and raw materials for compliance with IASC (International Aloe Science Council) certification requirements, specifically, for determination of the content of acetylated polysaccharides, the presence of glucose, the presence and content of maltodextrin, and the content of isocitrate. Additionally, for meeting quality control specifications beyond IASC requirements, the presence and content of the following groups of compounds can be determined: degradation products (e.g., lactic acid, pyruvic acid, succinic acid, fumaric acid, acetic acid, formic acid, and ethanol), preservatives (e.g., potassium sorbate, sodium benzoate, and citric acid/citrate), and other atypical impurities, additives, or adulterants (e.g., methanol, glycine, glycerol, sucrose, maltodextrin, flavorants (propylene glycol/ethanol)). We will describe a common internal-standard NMR methodology that does not require additional equipment or advanced automation software. The method is applicable to a number of different Aloe Vera raw materials and products, including liquid and dried juices. In aloe vera finished products the method is only applicable when the observable aloe vera constituents are present at a high enough concentration to be observed and are not obscured by additional product ingredients with signals in overlapping areas.

Poster 2

Compact, Cryogen-Free, High-Resolution 60 MHz Permanent Magnet NMR Systems for Reaction Monitoring and On-Line/At-Line Process Control Observing 1H, 19F, 31P

John C. Edwards1, Tal Cohen2, Paul J. Giammatteo1

1. Process NMR Associates, LLC Danbury, CT
2. Aspect AI, Shoham, Israel

A compact high resolution NMR system will be described that can be situated on the bench-top or in the fume hood to be used as a continuous or stop-flow detector and/or an “in-situ” reaction monitoring system. The same system can be fully integrated into on-line shelters for on-line process control or utilized by engineers and technicians in an “at-line” environment. The system uses a unique 1.5 Tesla permanent magnet that can accommodate sample tube diameters of 3-10 mm with half-height spectral resolution (water resonance) approaching 1-3 Hz depending on the sample volume size and with excellent single pulse sensitivity. These systems can be utilized in a traditional NMR methodology approach or combined with chemometric approaches that allow NMR data to predict chemical and physical properties of materials via regression analyses that establish correlations between observed spectral variability and sample-to-sample property variance [1].

1) “Process NMR Spectroscopy: Technology and On-line Applications”, John C. Edwards, and Paul J. Giammatteo, in Process Analytical Technology: Spectroscopic Tools and Implementation Strategies for the Chemical and Pharmaceutical Industries, 2nd Ed., Editor Katherine Bakeev, Blackwell-Wiley, 2010

Poster 3

Calculation of Average Molecular Descriptions of Heavy Petroleum Hydrocarbons by Combined Analysis by Quantitative 13C and DEPT-45 NMR Experiments

John Edwards Process NMR Associates, LLC, Danbury, CT

Much debate has centered around the validity and accuracy of NMR measurements to accurately describe the sample chemistry of heavy petroleum materials. Of particular issue has been the calculated size of aromatic ring systems that in general seem to be underestimated in size by NMR methods. This underestimation is principally caused by variance in chemical shift ranges used by researchers to define the aromatic carbon types observed in the 13C NMR spectrum, in particular the bridgehead aromatic carbons that can be shown to overlap strongly with the protonated aromatic carbons. The ability to discern between bridgehead aromatic carbons and protonated carbons in the 108-129.5 ppm region of the spectrum is key in the derivation of molecular parameters that describe the “molecular average” present in the sample. Utilizing methodologies developed by Pugmire and Solum for the solid-state 13C NMR analysis of coals and other carbonaceous solids we have developed a new liquid-state 13C NMR method that allows the relative quantification of overlapping protonated and bridgehead aromatic carbon signals to be determined. The NMR experiments involve the combined analysis of both quantitative 13C single pulse excitation which observes all carbons quantitatively, and a DEPT45 polarization transfer which observes only the protonated carbons in the sample. Though the DEPT45 results are not quantitative across all carbon types (CH, CH2, and CH3) due to polarization transfer differences, the technique is well enough understood that simple multiplication factors allow the relative intensities of the different carbons to be determined. The average ring system sizes derived from these NMR experiments tend to be several ring systems larger than has been calculated in previous studies. In heavy petroleum asphaltenes the average aromatic ring system is 5-7 rings in size which is in agreement with FTICR-MS and fluorescence measurements, rather than the 3-4 rings previously reported.

Process NMR Associates to Present 3 Posters at SMASH NMR Conference, September 9-12, 2012

News - John Edwards of Process NMR Associates will be presenting the following 3 posters at SMASH NMR Conference, Providence RI, September 9-12, 2012. Process NMR Associates will also have a vendor table where John will be available to discuss the exciting range of high and low resolution permanent magnet NMR products available through the company and it’s partners Aspect AI and Cosa-Xentaur.

Poster 1
Quantitative Proton Nuclear Magnetic Resonance Spectrometry (1H-NMR) for Determination of Acetylated Polysaccharides, Glucose, Maltodextrin, and Isocitrate in Aloe Vera Leaf Juice

John C. Edwards, Process NMR Associates, Danbury, Connecticut

Aloe Vera is a botanical component that is used widely in the cosmetic, natural product, herbal supplement, and pharmaceutical industries. The widespread use of Aloe Vera has lead to the need to adequately analyze the authenticity, quality, and quantity of the various components present in this material. The qNMR method described here was developed and validated by Process NMR Associates (Danbury, CT) and is similar to an independently validated method developed by Jiao et al [1]. The method described is to be included in an upcoming Monograph on Aloe Vera published by the American Herbal Pharmacopoeia. The method can be used for the detection and quantitation of the primary components of interest in Aloe Vera juice products and raw materials for compliance with IASC (International Aloe Science Council) certification requirements, specifically, for determination of the content of acetylated polysaccharides, the presence of glucose, the presence and content of maltodextrin, and the content of isocitrate. Additionally, for meeting quality control specifications beyond IASC requirements, the presence and content of the following groups of compounds can be determined: degradation products (e.g., lactic acid, pyruvic acid, succinic acid, fumaric acid, acetic acid, formic acid, and ethanol), preservatives (e.g., potassium sorbate, sodium benzoate, and citric acid/citrate), and other atypical impurities, additives, or adulterants (e.g., methanol, glycine, glycerol, sucrose, maltodextrin, flavorants (propylene glycol/ethanol)). We will describe a common internal-standard NMR methodology that does not require additional equipment or advanced automation software. The method is applicable to a number of different Aloe Vera raw materials and products, including liquid and dried juices. In aloe vera finished products the method is only applicable when the observable aloe vera constituents are present at a high enough concentration to be observed and are not obscured by additional product ingredients with signals in overlapping areas.

1. “Quantitative 1H-NMR spectrometry method for quality control of Aloe vera products”, Jiao, P., Jia, Q., Randel, G., Diehl, B., Weaver, S., Milligan, G., J AOAC Int., 93(3), 842-848, 2010

Poster 2
Practical Applications of Compact, Cryogen-Free High-Resolution 60 MHz Permanent Magnet NMR Systems for Reaction Monitoring and Online/At-Line Process Control

John C. Edwards, Process NMR Associates, LLC, 87A Sand Pit Road, Danbury, CT 06810 USA

For the past two decades high resolution 1H NMR at 60 MHz has been utilized to monitor the chemical physical properties of refinery and petrochemical feedstreams and products1. These approaches involve the use of partial least squares regression modelling to correlate NMR spectral variability with ASTM and other official test methods, allowing the NMR to predict results of physical property tests or GC analysis. The analysis is performed in a stop flow environment where solenoid valves are closed at the beginning of the NMR experiment. This approach allows up to 5 or 6 different sample streams to be sent to the sample in order to maximize the impact of the instrument. The current work with these permanent magnet NMR systems is to utilize them as chemistry detectors for bench-top reaction monitoring, mixing monitoring, dilution monitoring, or conversion monitoring. In the past use of NMR for these applications has been limited by the need to bring the “reaction” to the typical “superconducting” NMR lab. A compact high resolution NMR system will be described that can be situated on the bench-top or in the fume hood to be used as a continuous or stop-flow detector and/or an “in-situ” reaction monitoring system. The system uses a unique 1.5 Tesla permanent magnet that can accommodate sample diameters of 3-10 mm with half-height resolution approaching 1-3 Hz (depending on the sample size) and excellent single pulse sensitivity. Reaction monitoring can be performed using a simple flow cell analyzing total system volumes of 2 to 5 mL depending on the length and diameter of the transfer tubing. Further, detection limits of analytes in the 200+ ppm range are possible without the use of typical deuterated NMR solvents. Analysis times of 5 to 20 seconds are also possible at flow rates of 5 to 20+ ml/minute. Reaction monitoring directly in standard 5-10 mm NMR tubes using conventional (non-deuterated) reactants, solvents and analytes will also be described. Examples of 1H, 19F and 31P analyses will be described.

1.“Process NMR Spectroscopy: Technology and On-line Applications” John C. Edwards, and Paul J. Giammatteo, in Process Analytical Technology: Spectroscopic Tools and Implementation Strategies for the Chemical and Pharmaceutical Industries, 2nd Ed., Editor Katherine Bakeev, Blackwell-Wiley, 2010

Poster 3
Calculation of Average Molecular Descriptions of Heavy Petroleum Hydrocarbons by Combined Analysis by Quantitative 13C and DEPT-45 NMR Experiments

John C. Edwards

Process NMR Associates, LLC, 87A Sand Pit Rd, Danbury, CT 06810 USA

Over the years much debate has centered around the validity and accuracy of NMR measurements to accurately describe the sample chemistry of heavy petroleum materials. Of particular issue has been the calculated size of aromatic ring systems that in general seem to be underestimated in size by NMR methods. This underestimation is principally caused by variance in chemical shift ranges used by researchers to define the aromatic carbon types observed in the 13C NMR spectrum, in particular the bridgehead aromatic carbons that can be shown to overlap strongly with the protonated aromatic carbons. The ability to discern between bridgehead aromatic carbons and protonated carbons in the 108-129.5 ppm region of the spectrum is key in the derivation of molecular parameters that properly describe the “molecular average” present in the sample. Utilizing methodologies developed by Pugmire and Solum [1] for the solid-state 13C NMR analysis of coals and other carbonaceous solids we have developed a new liquid-state 13C NMR method that allows the relative quantification of overlapping protonated and bridgehead aromatic carbon signals to be determined [2]. The NMR experiments involve the combined analysis of both quantitative 13C single pulse excitation which observes “all carbons in the sample” and DEPT45 polarization transfer which observes only the protonated carbons in the sample. Though the DEPT45 results are not quantitative across all carbon types (CH, CH2, and CH3) due to polarization transfer differences, the technique is well enough understood that simple multiplication factors allow the relative intensities of the different carbons to be determined. An additional aspect of the experiments is the addition of a standard material (PEG polymer) that allows the calculation of the absolute percentage of the carbons observed by the NMR technique. This allows the relative amount of bridgehead carbon to be calculated by direct comparison of the aromatic region with the standard signal intensity. The average ring system sizes derived from these NMR experiments tend to be several ring systems larger than has been calculated in previous studies. In asphaltenes for example the ring systems are 5-7 rings in size rather than the 3-4 rings reported previously. The ring sizes determined by this new combined NMR method are in agreement with FTICR-MS and fluorescence measurements.

1) “Carbon-13 Solid-State NMR of Argonne Premium Coals”, Mark S. Solum, R.J. Pugmire, David M. Grant, Energy Fuels, 1989, 3(2), pp 187-193

2)” Comparison of Coal-Derived and Petroleum Asphaltenes by 13C Nuclear Magnetic Resonance, DEPT, and XRS”, A. Ballard Andrews, John C. Edwards, Andrew E. Pomerantz, Oliver C. Mullins, Dennis Nordlund, and Koyo Norinaga, Energy Fuels, 2011, 25 (7), pp 3068–3076

Process NMR (High, Mid and Low Resolution) Session at Practical Applications of NMR in Industry Conference

John Edwards (PNA) and Mark Zell (Pfizer) are co-chairs of a session of practical NMR applications in process control, reaction monitoring, miniaturized instrumentation, TD-NMR. John Edwards is also co-chairing a session (with Kathleen Farley of Pfizer) on quantitative NMR that contains an excellent talk on quantitative online NMR spectroscopy. Speakers in our sessions include:

Session: On-Line/In-Line NMR and Time-Domain NMR
Session Chairs: John Edwards, Process NMR Associates and Mark Zell, Pfizer, Inc.

On-Line Applications of High-Resolution NMR in the Petroleum Industry – Direct Measurement, Chemometric Correlation, and Multiple Spectroscopy Data Fusion – John Edwards, Process NMR Associates, Danbury, CT USA

Online NMR Reaction Monitoring in Pharmaceutical Process Development – David Foley, Pfizer Global Research and Development, Groton, CT USA

Beyond Hammers in Search of Nails: An instrument technologist’s perspective on developing miniaturized NMR spectrometers for new applications – Andrew McDowell, ABQMR, Inc., Albuquerque, NM USA

LF-NMR Studies of Mechanically Induced Gel Syneresis in Cheese – Soren Engelsen, University of Copenhagen, Frederiksberg, Denmark

NMR Quantification of Structural Features in Food Science and Technology – John van Duynhoven, Unilever – Vlaardingen, The Netherlands

Rheological Measurements on Non-Newtonian Fluids Using a Process Compatible MRI – Michael McCarthy, University of California at Davis, Davis, CA USA

Session: Quantitation Applications 2
Session Chairs: John Edwards, Process NMR Associates and Kathleen Farley, Pfizer, Inc.

High Precision Purity Determination by qNMR – How to Achieve an Uncertainty of Measurement of 0.15%? – Torsten Schonberger, Federal Criminal Police Office (“Forensic Science Institute” (Bundeskriminalamt, BKA) Wiesbaden, Germany

Process Analytical Applications of Quantitative Online NMR Spectroscopy – Michael Maiwald, BAM, Federal Institute for Materials Research and Testing, Berlin, Germany

The entire scientific program for the conference can be found here – PANIC Scientific Program

Practical Applications of NMR in Industry Conference (PANIC) – Student Travel Grants Available

CASSS is pleased to provide a limited number of student travel grants for PhD students and post-docs who present posters at the Practical Applications of Nuclear Magnetic Resonance Conference (PANIC). PhD students or post-doctoral fellows conducting research with professors in universities throughout the world are eligible.

CASSS would like to gratefully acknowledge the Suraj Manrao Student Travel Science Fund for their contribution to subsidize one additional science student to attend the PANIC Conference.

To apply for a student travel grant, students should submit:

Your abstract online (Please click here to submit your abstract)

A letter requesting consideration for the grant

A letter of recommendation from your professor or advisor

A PDF of your abstract

A CV for the candidate

All documents can be emailed to the NMR Symposium Manager, Linda Mansouria at lmansouria@casss.org. The deadline to apply for a student travel grant is Friday, July 13, 2012.

Newsflash: For Immediate Release – Process NMR Associates and Quantum Tessera Enter into Strategic Partnership

Process NMR Associates, LLC, Danbury, CT and Quantum Tessera Consulting, LLC, Collegeville, PA, USA

Process NMR Associates, LLC (LLC) and Quantum Tessera Consulting, LLC are pleased to announce they have entered into a Strategic Partnership. This partnership will leverage PNA’s experience applying magnetic resonance techniques to such processes as reaction monitoring, active ingredient quality control, and the petroleum industry. PNA’s MR expertise extends into time-domain NMR, low field high resolution NMR (60MHz and 300MHz) applications, and chemometrics. Quantum Tessera brings its knowledge and experience about large molecule process development. Together, Process NMR Associates and Quantum Tessera can deliver higher value to clients process and manufacturing problems.

Process NMR Associates and Quantum Tessera’s first project will be focused initially on NMR-based solutions for bioprocess monitoring and biofuel manufacture.

Dr. John Edwards, Principal and Manager of Analytical Services at PNA comments, “The combination of Quantum Tessera Consulting and PNA will allow both companies to expand their customer base and allow them to offer a wider range of robust and innovative solutions to our clients.”

Dr. Edward Zartler, CSO of Quantum Tessera, adds, “Process NMR associates has always led the field in NMR-based process analytics. This Strategic Partnership will result in synergies between our two companies, where the sum will be greater than the individual parts.”

About Quantum Tessera Consulting, LLC (http://www.quantumtessera.com): Quantum Tessera provides complete analytical solutions to its clients. While focused on NMR-based solutions, Quantum Tessera is focused on delivering the most appropriate solution to its customers. Quantum Tessera is focused on two major areas: Fragment-based Drug Discovery (FBDD) and Bioprocess Development.

About Process NMR Associates, LLC (http://www.process-nmr.com/): Process NMR Associates provides 1) 300 MHz analytical NMR services and consulting, 2) sales and marketing of the Aspect Italia 60 MHz high resolution NMR systems for process analytical and laboratory applications, and 3) marketing, sales, and applications for the Cosa-Xentaur SpinPulse TD-NMR spectrometer series.

The Power of MestReNova Data Processing and Analysis Applied to 60 MHz 1H NMR Real Time Reaction Monitoring

The data analysis capabilities of the MestReNova NMR software makes processing and analyzing complex reaction mixture data a snap! Stacked plots are quick and easy and the integration routines rapidly process the peak areas into reaction profiles. Further steps allow the exponential fitting of the reaction profiles to yield kinetic information. Here are a few examples of the data visualization and rapid reaction profiling on a 60 MHz 1H NMR series obtained every 10 seconds (1 pulse) over the course of 25 minutes – the reaction is the esterification of tert-butanol with acetic anhydride in the presence of acid.

1H NMR Superimposed Plot  - Reaction Monitoring
Figure 1: Stacked Plot of the Aliphatic Region of the Spectrum with Reaction Chemistry Protons Identified

Stacked Plot - 1H NMR Spectra - Reaction Monitoring
Figure 2: Stacked Plot – Full Spectrum – Reaction Monitoring – 146 Spectra – 10 Seconds Apart

Stacked and Angled Stacked Plot - 1H NMR - Reaction Monitoring
Figure 3: Angled Stack Plot – Acetic Anhydride and tert-Butanol – Real Time Reaction Monitoring by 1H NMR at 60 MHz

Whitewashed Stacked Plot - 1H NMR Spectra - Aliphatic Region - Reaction Monitoring
Figure 4: Stacked and Whitewashed Plot of 1H NMR data at 60 MHz – Real Time Reaction Monitoring of Acetic Anhydride with tert-Butanol

Integrated Stacked Plot with Reaction Profiles Obtained from MNova Data Analysis
Figure 5: Data Analysis Tool and production of reaction profiles.

The MNova data analysis tools allow the user to integrate NMR reaction peaks and automatically plots and fits them to exponential time constants allowing detailed kinetics to be extracted rapidly and easily from the data. What used to take hours of lining up ascii spectra in excel or other software now literally takes seconds. The integration is segmented in such a manner that integrals can be made to track with shifting resonances, for example labile protons effected by pH.

The AspectItalia 60 MHz NMR system allows real time analysis of reactions with high S/N on single pulses. half height linewidths of 1-2 Hz (15-30 ppb) are possible on static reaction setups and 2-5 Hz (30 – 80 ppb) are possible with flowing reactions at rates of 1-20 ml/min.

The MNova software is becoming a standard NMR processing platform with many users worldwide. Fully functioning demos can be downloaded from the MestReLab research site at: http://mestrelab.com/software/mnova-nmr/

For further details contact John Edwards

Cryogen-Free NMR – High Resolution Permanent Magnet Systems – The Market Hots Up

It is interesting times in the world of NMR – there are a number of new permanent magnet NMR systems hitting the market. I have seen a number of announcements appearing on LinkedIn and other sites in recent days and then there was a question asked about Cryogen-free NMR systems on the AMMRL server. There is a little confusion out there about who is doing what and what these newer NMR systems are capable of. We (Process NMR Associates and Aspect Italia) have been in the market with a high resolution 60 MHz system (3, 5, or 10mm sample tube) since 1997. Anasazi Instruments have been quitely selling hundreds of 60 and 90 MHz FT-NMR systems based on refurbished or newly manufactured Varian EM-360 and EM-390. New to the scene and making a splash with their marketing campaigns are Picospin (300 micron sample tube, 45 Mhz), Nanalysis (3, 5mm sample tube, 60 MHz). Finally, there is a system from Magritek/ACT (5mm sample tube, 42.5 MHz) that has been re-packaged and is now out there in the world. These systems all produce spectra and can be used in the traditional manner that current supercon systems are utilized. Time-Domain (TD) NMR systems should not be confused with these platforms – TD-NMR spectrometer manufacturers include Cosa-Xentaur, Bruker, Oxford Instruments, SpinLock, MR-Resources – which are used typically for hydrogen content, rheology, simple phase measurements (solid fat, water in oil, oil in water, porosity measurements utilizing relaxation analysis.

For the past 17 years we have been actively developing applications for permanent magnet systems shimmed to approximately 3 Hz at peak half height. The current magnet technology is in its third generation of development and the magnets are built by Aspect Italia and subsidiary of Aspect Imaging who are making an impact with their industrial and clinical MRI systems (Aspect is also working in collaboration with Bruker on their Icon MRI system). The new magnet design is robust and readily shims to 1-2 Hz at half height using 5 or 3 mm NMR tubes. 3 Hz at half height is possible for 10 mm NMR tubes. In the past the focus was in on-line applications in refining and petrochemical and lab systems were not actively marketed. With the third generation of NMR instrument it is time for these robust, non-cryogen, permanent magnet systems to be applied in laboratory and general quality testing applications.

In our laboratory we have an application development advantage in that we have high field 300 MHz NMR systems that are active in commercial NMR analysis and in high field method development. We also have ESR, FTIR-ATR, GC, moisture measurements, and other instruments that we can bring to bear on applications. We can readily develop 60 MHz applications using the 300 MHz NMR data as the basis set to provide primary parameters for analysis or to answer questions about the spectral overlaps that inevitably occur in 60 MHz data sets where 1 ppm on the spectrum axis represents only 60 Hz rather than 300 Hz. When a high field NMR spectroscopist observes a data comparison of spectra obtained at 60 MHz to the same spectrum obtained at 300 MHz (a resolution that most are familiar with) the penny suddenly drops concerning the possibilities that exist for NMR analysis at this field and an appreciation for the work that was performed for the first 30 years of NMR technology on 40 and 60 MHz CW NMR’s. We have become accustomed to our big supercon magnets and have forgotten what can be accomplished at 60 MHz. In these days of powerful computers for multivariate analysis and the ability ot perform global spectral deconvolution (GSD) the ability to develop killer-apps for bench-top, at-line, or in-line applications of 1H/31P/19F/23Na/11B NMR for 110V powered systems is here. The application of chemometrics and GSD at 60 MHz can allow the lower resolution issue of peak overlap to be overcome.

In the past few days I have been “playing around” with the two Aspect systems we have in our lab – comparing spectra obtained on our 300 MHz systems to the same samples on the 60 Mhz systems. Direct comparisons of the data make you realize that though the resolution isn’t anywhere near the same – the information is present in the 60 MHz spectrum. In the links below I have included a number of PDFs showing comparisons of complex essential oil spectra, fish oil and vegetable oils (looking at omega-3 fatty acid content), polyurethane adhesive polymers, shale oil, gasoline and a spectrum of Poloxamer which is a oxyethylene-oxypropylene copolymer utilized in the pharmaceutical industry that has an NMR based USP/NF method associated with it to determine the oxyethylene content.

Polyurethane Polymers – 60 MHz vs 300 MHz – PDF

Essential Oils – 60 MHz vs 300 MHz – PDF

Fish Oils and Seed Oils – Omega-3 Content – 60 MHz vs 300 MHz – PDF

Poloxamer Analysis – Shale Oil and Gasoline Analysis – 60 MHz vs 300 MHz – PDF

Aspect Italia - 60 MHz Benchtop Laboratory NMR system

Process NMR is actively involved in development of NMR applications utilizing 60 MHz or 300 MHz NMR data. We can develop applications for you and also provide the robust, proven instrumentation that can make affordable, cryogen-free NMR analysis a common automated laboratory tool. We are also looking to prove the utility of this excellent technology in all industrial sectors – if you have an application and would like to see a feasibility study we would be happy to provide such an opportunity. We have NMR systems looking for things to do! Please contact us if you feel you have an application where NMR may provide an answer through direct measurement or chemometric calibration. We are also interested in developing multi-spectroscopy technique data fusion applications where NMR and IR are combined to provide “better answers”.

Anita Brandolini – NMR Spectroscopist and Professor – RIP

We saddened to hear today that our good friend and NMR compatriot Anita Brandolini passed away a few weeks ago. We were informed by Mike Frey of JEOL that the North Jersey Section of ACS will be setting up a memorial as part of Project SEED. If you knew Anita or share her passion for teaching science to the young then please consider donating to this cause.

Anita J.Brandolini, 56, Assistant Professor of Chemistry at Ramapo College of New Jersey, died suddenly at her home in Hillsboro, NJ on March 10, 2012.
Originally from Morton, PA, Brandolini earned her B.S. in Chemistry in 1979 at Drexel University and her M.A. and PhD in Physical Chemistry in 1981 and 1983 at the University of Delaware. She was also a course Instructor for JEOL, USA, Inc.

Brandolini worked for 17 years at Mobil Chemical where she was a Team Leader and Senior Research Chemist in polymer analytical chemistry. She was an expert in the nuclear magnetic resonance of polymer systems publishing a book, NMR Spectra of Polymers and Polymer Additives (Anita J. Brandolini and Deborah D. Hills, New York; Marcel Decker, 2000) and contributing chapters on spectroscopy to numerous publications.

In 2000 Brandolini began a full time academic career accepting a two-year appointment at the College of New Jersey and then teaching at William Paterson University and Fairleigh Dickinson University before joining the Ramapo University faculty in 2007. She was an enthusiastic educator dedicated to undergraduate teaching and research and incorporating her industrial experience into her teaching, design of experiments, and writing. She believed strongly in undergraduate research and mentored many students. Her work primarily involved studies of the adsorption of polymers to surfaces and, more recently, the binding of dyes to nucleic acids.

Brandolini disseminated her love of chemistry broadly. She published a book for children Fizz, Bubble, and Flash: Element Explorations and Atom Adventures (Anita J.Brandolini, Charlotte, VT. Williamson Books, 2003) for which she was awarded the Parents’ Choice Foundation Silver Honor in 2003. She developed a website Keys to Chemistry, an interactive forum for students to practice chemistry, and she hosted a blog Dr. B’s Science Lab where she posted monthly themed experiments involving science for the whole family. She also gave many lectures at schools and at the New Jersey Liberty Science Center.

Brandolini was an active member of the ACS and its North Jersey Section. She was an ACS Councilor and served as Secretary and Chair of the Section. Nationally she was a member of the Committee on Project SEED and the Committee on Public Relations and Communications. In 2011 she was named a Fellow of the American Chemical Society.

The NJACS is establishing an Annual Project SEED Award to be given to an outstanding high school student at the SEED Poster Session held in September each year.

Donations to the Anita J. Brandolini SEED Fund should be sent to the following address:
Val Kuck
NJACS Project SEED Treasurer
45 Warfield St
Upper Montclair, NJ 07043

Please make checks payable to NJ Project SEED and in memo include The Anita J. Brandolini Fund.

Whole Leaf Marker and Maltodextrin in Aloe Vera Raw Materials – Dry Weight Quantity – Extended 1H NMR Analysis Method

Process NMR Associates has developed an extension of its 1H NMR analysis of Aloe Vera raw materials and products analysis. Powder aloe vera raw materials (100x/200x) can be analyzed directly and juice samples (1x, 5x, 10x, commercial products) must be freeze dried for this analysis. The whole leaf markers utilized in this test to indicate the presence of whole leaf material are iso-citrate and iso-citrate lactone which are formed in the green leaf part of the aloe plant as part of the citric acid cycle. It is possible to assign and quantify the following components of an aloe vera juice or powder:

* aloe vera components: acemannan, glucose, malic acid
* whole leaf markers: isocitrate, iso-citrate lactone, citric acid
* degradation products: lactic acid, acetic acid, fumaric acid, pyruvic acid, formic acid, succinic acid, and ethanol
* adulterants: maltodextrin
* preservatives: sorbate, benzoate
* additives: sucrose, fructose, glycine, flavorants (contain ethanol and propylene glycol)

For the components above it is possible to obtain a wt% of that component in a juice sample – the freeze drying process is then used to determine the wt% solids in the juice and the dry weight concentrations of the organic components in the solids.

Currently testing of aloe vera raw materials revolve around acemannan and whole leaf marker content and the presence of glucose. Process NMR Associates method can perform this analysis but also tell you the “quality” of the aloe vera raw material – the absolute concentrations of degradation products can tell you a lot about the exposure of the raw material to:

* excessive heat (hydrolyzation of acemannan acetyl groups to acetic acid (vinegar) or formic acid)
* lactobacillus bacteria (found on the skin of the aloe vera plant – these bacteria “eat” malic acid and produce lactic acid)
* enzymatic processes (enzymes found in the aloe vera plant itself can cause degradation to succinic acid or fumaric acid

The figure below shows the NMR assignment of a whole leaf juice that has been freeze dried. From the molar ratios of the various 1H NMR peaks it is possible to obtain a wt% value for all components by comparison with a nicotinamide internal standard (spectral range not shown) and the molecular weight of the component molecule or monomer unit.

Whole Leaf Marker and Adulteration Analysis of Aloe Vera Raw Materials

1H NMR spectroscopy observes signals from all protons in the sample simultaneously. Aloe vera components, preservatives, and degradation products yield peaks at specific chemical shifts which can be integrated and quantified. Observations are made on the following peaks:

Nicotinamide – Internal NMR Standard: 1) 8.85 ppm, 2) 8.2 ppm (often coincides with formic acid), 3) 7.55 ppm, 4) 8.65 ppm
Glucose – C1 proton for alpha conformation at 5.2 ppm (doublet) and C1 proton for beta conformation at 4.6 ppm (doublet)
Malic Acid – CH at 4.35 ppm (multiplet), CH2 at 2.4-2.8 ppm (multiplet)
Acemannan – CH3 resonances of acemannan acetylation – fingerprint distribution of methyl resonances from 2.0-2.2 ppm
Lactic Acid – CH3 Peak at 1.33 ppm (doublet)
Acetic Acid – CH3 peak at 1.92 ppm (singlet)
Succinic Acid – 2 x CH2 peak at 2.5 ppm (singlet)
Formic Acid – Aldehyde Resonance at 8.2 ppm (singlet)
Ethanol – CH3 peak at 1.18 ppm (triplet)
Pyruvic Acid – CH3 peak at 2.35 ppm (singlet)
Citric Acid – 2 x CH2 resonances at 2.4 to 3.0 ppm (multiplet)
Iso-Citrate (Whole Leaf Marker) – CH at 4.25 ppm (doublet)
Iso-Citrate Lactone (Whole Leaf Marker) – CH at 5.05 ppm (doublet)
Benzoate – ortho-protons (2H) give peaks at 7.8 ppm.
Sorbate – CH3 peak is observed at 1.77 ppm (doublet) olefin protons observed at 5.7, 6.15, &7 ppm.
Fumaric Acid – CH peak at 6.55 ppm (singlet)
Sucrose – C1 proton observed at 5.4 ppm (doublet)
Maltodextrin – qNMR protons observed at 5.4 ppm

Maltodextrin is readily observed and quantified by 1H NMR – in the figure below is an example of a 100x and a 200x aloe vera gel powder – the 100x sample contains 50 wt% maltodextrin – the peaks at 5.4 and in the 3.5-4.0 ppm region are used to quantify the presence of maltodextrin.

Maltodextrin Adulteration - 1H NMR Test -  Aloe Vera Raw Material Testing

Process NMR Associates is currently the only company providing a detailed breakdown of the components of aloe vera including quantitation of the whole leaf markers. Dry weight limits of acemannan, whole leaf markers, and maltodextrin are required for aloe vera raw material certification and quality control.

In the food industry it is found that most fruits, beverages, and dairy products contain a complex mixture of these same organic acid chemistry components. 1H NMR has a unique advantage in the analysis of these types of materials as NMR requires very little sample preparation and the data can be used to unequivocally identify the presence of single component chemistries and to quantify their presence in a single 15-30 minute analysis. Process NMR Associates are available to develop NMR based methodologies on any of these types of food systems and would welcome discussion of this with potential customers. Customers are not charged for initial consultation and project scoping. These NMR methods are universally applicable on NMR systems from 200-900 MHz. If you are interested please contact John Edwards (Tel: +1 (203) 744-5905)

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Talks to be Presented at IFPAC 2012 – Baltimore, MD January 22-25

Talk 1 by John Edwards

Mutivariate Analysis of 1H and 13C NMR Data of Residual Catalytic Cracker Feed-Streams: NMR Pre-Processing Strategies that Allow the Development of Predictive Models of Physical and Chemical Properties that are Independent of NMR Instrument Magnetic Field Strength

John C. Edwards*# and Jincheol Kim†
*Process NMR Associates, LLC, 87A Sand Pit Rd, Danbury, CT 06810 USA
† SK Innovation Co., Ltd, SK Innovation Technology Center, 140-1, Wonchon-dong, Yuseong-gu, Daejeon 305-712, Korea
# Speaker

Historically refinery control engineers are familiar with GC derived chemical properties such as aromatics, benzene, PONA, olefins in wt% or vol%, as well as physical properties such as distillation, viscosity, conradson carbon, sulfur, density, etc. We have developed generally applicable multivariate regression methods that allow many of these familiar chemical and physical properties to be derived from quantitative 1H or 13C NMR data. We have also developed magnetic field independent data manipulation methods that allow 1H or 13C NMR derived parameters to be utilized as the X matrix “spectral” data rather than the spectra themselves. This allows field independent models to be developed as these parameters are calculated from the spectrum and are the same regardless of the magnetic field strength at which the NMR data was collected. This has implications with respect to calibration transfer between laboratories and analyzers. In this work we describe the application of these methods to feed-streams to a residual catalytic cracker (RCC), which represents the core gasoline and diesel production facility in many refineries.

Talk 2 by Paul Giammatteo

Practical Applications of Compact High-Resolution 60 MHz Permanent Magnet NMR Systems for Reaction Monitoring and Online Process Control

John Edwards*, Paul Giammatteo*#, Mark Zell†, and David Foley†
* Process NMR Associates, 87A Sand Pit Rd, Danbury, CT, 06810 USA
† Pfizer Global Research and Development, Groton Laboratories, Eastern Point Road, Groton, CT 06340 USA
# Speaker

Process NMR Associates will be exhibiting the Spin Pulse range of TD-NMR spectrometers as well as the Aspect Italia 60 MHz high resolution NMR system – See us at the Cosa-Xentaur booth in the exhibition.

For more details on IFPAC visit http://www.ifpac.com/

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New Conference Being Planned for Practical Applications of NMR in Industry

CASSS announces the first Practical Applications of NMR Conference 2012. Save the Date: October 15-17, 2012. The conference will be held at the Hyatt Regency Schaumberg, Schaumberg, IL USA. John Edwards has volunteered to serve on the organizing committee and will be developing a session of talks on on-line/at-line NMR and TD-NMR technologies. Other exciting sessions will revolve around other practical NMR applications in industry – more details will be posted when the program has been developed further.

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1H NMR – 60 MHz Permanent Magnet System – Reaction Monitoring

Below are a few further examples of acetylation reactions of acetic anhydride with an excess of alcohol. The alcohols include tert-butanol and isopropanol.

Reaction 1: Acetylation of t-butyl alcohol with acetic anhydride in the presence of acid.

Acetylation of t-butanol with acetic anhydride - 1H NMR Reaction Monitoring

Reaction 2: Acetylation of Isopropanol with acetic anhydride in the presence of acid.

Acetylation of isopropanol with acetic anhydride - 1H NMR Reaction Monitoring

Reaction 3: Methoxyacetone and hydroxylamine reaction in methanol to form an Oxime

Oxime Production from Ketone and Hydroxylamine - 1H NMR Reaction Monitoring

Oxime Production from Ketone and Hydroxylamine - Zoomed spectrum - 1H NMR Reaction Monitoring

Resolution of the methylenes in the methoxyacetone and the reaction product is readily observed.

Oxime from ketone and hydroxylamine - assignment - 1H NMR Reaction Monitoring

All the above experiments were performed in an NMR tube. We are currently looking at the same reactions under flow conditions utilizing a HPLC pump and PEEK tubing to transport sample to the NMR probe at 5 ml/min.

New Generation NMR Process Analyser from Modcon and Aspect

Modcon Systems (Israel) introduces the MOD-8000, a new generation of Nuclei Magnetic Resonance (NMR) process analyser. A new concept in the design of the magnet, the electronics and the software was implemented, alongside a suitable sampling system. High reliability and accuracy is achieved by eliminating sensitivity towards any temperature fluctuations.

Process streams with different temperatures and flow properties can accurately be analysed by one single instrument.

NMR is a fundamental method; it is based on the assignment and/or quantification of the chemical components and functionalities that are present in a refinery or petrochemical process stream. The linear spectral response enables chemometric methods to quantify accurately the required physical and chemical properties of process streams.

In contrast to optical correlative methods, its accuracy is not influenced by the presence of substances with atoms others than hydrogen and carbon which vary according to the origin of crude oils. Crude switching will not have any impact on the analytical results.

New Generation of Process NMR Analyzers from Modcon, Apsect, and Process NMR Associates

The MOD-8000 NMR process analyser is applicable to transparent, dense and opaque solutions alike. On-line analyses of crude oil, the entire range of distillates, and a variety of refinery streams, providing a highly effective tool in meeting the challenges of ongoing process optimisation and control.

Further Details

Application Possibilities

For details on the MOD-8000 NMR analyzer contact Paul Giammatteo – Tel: +1 (203) 744-5905

 

Selective Observation of High Resolution 19F Spectrum by 1.4 Tesla Process NMR System

Below is an example of a 19F NMR Spectrum obtained at 54.6 MHz on a 1.4 Tesla permanent magnet-based NMR System.

This is a 2 minute spectrum obtained by co-averaging 16 FIDs after zero-fill, autophase, referencing of each individual FID. The NMR system is not locked. No apodization of the NMR FID data was performed.

19F NMR Analysis by Process NMR Spectrometer

For more details on potential applications of 19F NMR please contact John Edwards (Tel: +1 203-744-5905)

 

Chevron Installs Low Field NMR Application: 31P NMR Analysis of Phosphoric Acid Strength in Alkylation Process

New Flash: Chevron purchases high resolution 31P NMR system for at-line analysis of a phosphoric acid catalyzed alkylation process.

The Chevron Richmond Refinery needed a simple and quick measurement of phosphoric acid strength and quality. Prior analysis procedures included transporting samples several miles from the refinery process to the technical center in order to perform the 31P NMR analysis on a high field superconducting NMR system. This process was also complicated by the fact that the process operators were not able to perform the analyses on the conventional high field NMR systems (400 MHz for 1H, 161 MHz for 31P) themselves, but had to wait for NMR technician and instrument availability. If sample analyses was required after research facility working hours the NMR lab technicians were required to come in and run the NMR for the process operators.

A simple permanent magnet bench-top NMR system has now been placed in the existing process lab adjacent to the process unit control room. The NMR samples are placed in specially designed 9 mm (diameter) x 50 mm (length) sample tubes in order to accommodate sample handling issues (high viscosity sample with no solvents being added) and are place easily into the NMR probe. Sample preparation is essentially non-existent and sample waste is minimal. The 31P NMR analysis itself takes around 3 minutes to perform.

The “at-line” NMR system is a high resolution Qualion permanent magnet system operating at 58.3 MHz for 1H and 24.2 MHz for 31P. The system is located on a lab bench in the process lab building. Some examples of the system performance are shown along with the comparison with high field NMR results. It can be seen that the lower field instrument provides more than adequate resolution to perform the acid strength analysis.

31P NMR - Orthophosphoric Acid

Figure 1: 31P NMR of 85% Phosphoric Acid

Figures 1 and 2 show quantitative 31P NMR spectra of different phosphoric acid concentrations dissolved in water. The NMR analysis is found to be fully quantitative.

31P NMR of Different Concentrations of H3PO4 in Water - At-Line NMR

Figure 2: 31P NMR signal acquired at 24.2 MHz on several concentrations of phosphoric acid in water.

Figure 3 shows the 31P NMR data obtained at 7 Tesla (121 MHz) and 1.4 Tesla (24.2 MHz) of actual process samples. The peak at 0 ppm corresponds to orthophosphoric acid, the peak at -15 ppm corresponds to the terminal P atoms of a polyphosphoric acid chain, and the peak at -30 ppm corresponds to internal P atoms in the middle of polyphosphoric acid chains. Relative areas of these peaks are used to calculate the acid strength.

31P NMR - Phosphoric Acid Strength - At-Line Assay

Figure 3: High field and low field 31P NMR spectra of Used Phosphoric Acid from Alkylation Process

Used Phosphoric Acid - At-Line 31P NMR Analysis

Figure 4: 31P NMR spectra and calculated acid strengths obtained on 3 different used phosphoric acid samples

Used Phosphoric Acid - At-Line 31P NMR - Acid Strength Assay

Figure 5: Another comparison of 7 Tesla laboratory acquired NMR data compared to rapid at-line 1.4 Tesla NMR assay of phosphoric acid strength.

The NMR system being utilized at the Chevron Richmond refinery is a Qualion 60 MHz NMR system utilizing a 31P probe.

For further details or to discuss your own NMR applications please contact Paul Giammatteo (Tel: +1 203-744-5905)

 

A Review of Applications of NMR Spectroscopy in the Petroleum Industry

John Edwards, principal of Process NMR Associates has authored a chapter entitled “A Review of Applications of NMR Spectroscopy in the Petroleum Industry” which appears in a new ASTM publication: Monograph 9 – Spectroscopic Analysis of Petroleum Products and Lubricants, Edited by Kishore Nadkarni. The chapter describes the application of high resolution 1H and 13C NMR, 1H TD-NMR, and solid-state NMR to petroleum chemistry and refining.

Monograph 9: Spectroscopic Analysis of Petroleum Products and Lubricants

The book can be ordered at the ASTM Bookstore.

RSC Symposium on Reaction Monitoring by NMR and Vibrational Spectroscopy

The presentations from the RSC symposium have been posted for download the RSC site at:

http://www.rsc.org/ConferencesAndEvents/RSCConferences/Reaction/speakers.asp

COSA Xentaur Instrument Corporation and Process NMR Associates, LLC sign Application Development Agreement

COSA Xentaur Corporation, the company that specializes in high technology analyzers for a wide range of applications in petrochemical, energy, environmental, pharmaceutical, semiconductor and plastics industries, has joined with Process NMR Associates, LLC (PNA) as its application development partner for Cosa Xentaur’s new spectroscopy based products lines. Initial development will be a Time Domain Nuclear Magnetic Resonance (TD -NMR) to be introduced at PittCon 2011 in March.

COSA Xentaur is focused on providing innovative measurement solutions to a wide range of analytical and process applications. It is COSA Xentaur’s philosophy to supply industrial and laboratory users with cutting edge technology in a reliable and affordable instrument with full application engineering and service support.

PNA provides solution based applications for a wide range of spectroscopy platforms. These include on-line, at-line, and laboratory automated analyses that are utilized worldwide in petroleum refineries, petrochemical, chemical, and food manufacturing. “Process NMR Associates is pleased to form this partnership with COSA Xentaur,” said Paul Giammatteo, Operations Manager. “This commitment enables both companies to deliver incomparable, solution driven applications on quality instrument platforms to meet the changing needs of analytical laboratories in a number of industries.”

Reaction Monitoring Using NMR and Vibrational Spectroscopy – RSC Conference

Dr. John Edwards of Process NMR Associates will be attending an RSC sponsored one day symposium on “Reaction Monitoring Using NMR and Vibrational spectroscopy – An Industrial Perspective”. The meeting will be held at the Pfizer Research Center in Sandwich, Kent, UK on March 22, 2011. Dr Edwards will be presenting a poster entitled “Practical Applications of Compact High-Resolution 60 MHz Permanent Magnet NMR Systems for Reaction Monitoring and Online Process Control”. The abstract of the talk is presented below:

For the past two decades high resolution 1H NMR at 60 MHz has been utilized to monitor the chemical physical properties of refinery and petrochemical feed-streams and products. These approaches involve the use of partial least squares regression modeling to correlate NMR spectral variability with ASTM and other official test methods, allowing the NMR to predict results of physical property tests or GC analysis. The analysis is performed in a stop flow environment where solenoid valves are closed at the beginning of the NMR experiment. This approach allows up to 5 or 6 different sample streams to be sent to the sample in order to maximize the impact of the instrument. The current work with these permanent magnet NMR systems is to utilize them as chemistry detectors for bench-top reaction monitoring, mixing monitoring, dilution monitoring, or conversion monitoring. In the past use of NMR for these applications has been limited by the need to bring the “reaction” to the typical “superconducting” NMR lab. A compact high resolution NMR system will be described that can be situated on the bench-top or in the fume hood to be used as a continuous or stop-flow detector and/or an “in-situ” reaction monitoring system. The system uses a unique 1.5 Tesla permanent magnet with a simple flow cell and total system volumes of 2 to 5 ml depending on the length and diameter of the transfer tubing. Further, detection limits of analytes in the 200+ ppm range are possible without the use of typical deuterated NMR solvents. Analysis times of 5 to 20 seconds are also possible at flow rates of 5 to 20+ ml/minute. Reaction monitoring directly in standard 5 mm NMR tubes again using conventional (non-deuterated) reactants, solvents and analytes will also be described.

Details of the symposium and registration information can be found at the RSC website.

Process NMR Associates Expands and Updates NMR Testing Facilities

Process NMR Associates has just finished completion of a complete update and expansion of the NMR facilities at it’s Danbury CT location. The faithful Varian Unity-300 spectrometer has been replaced by a Mercury-300 VX spectrometer and a second 300 MHz Mercury Plus system has been installed. This second 300 MHz NMR includes PFG and an indirect detection probe. These instruments compliment a Varian UnityPlus-200 spectrometer equipped with a 7 mm Solid-State MAS probe for analysis of solid materials. The doubling of the liquid-state NMR capacity will allow rapid turnaround of all sample submissions and expand the experimental capabilities of the facility.

Process NMR Associates is a private corporation providing analytical NMR services and consulting since 1997. The NMR facility in Danbury includes two 300 MHz, one 200 MHz, and two 60 MHz high resolution NMR spectrometers. The facility also houses a 10mm, 18mm, and 40mm TD-NMR facility for relaxation studies. The company also has gas chromatography, micro-ESR, and FTIR-ATR capabilities. For details of the analytical services provided please contact John Edwards.

The Role of NMR in FDA Mandated Identity Testing of Nutritional Supplements

Process NMR Associates Offers Testing, Consultation, and Support in Meeting Your Identity Testing, Laboratory Methodology, and Process Analytical Requirements for FDA DS CGMP Rule Compliance.

In conjunction with 21 CFR 111, the FDA’s Office of Nutrition, Labeling and Dietary Supplements has instituted the Dietary Supplement Current Good Manufacturing Practice Rule (DS GCMP Rule) and the Interim Final Rule effective December 2010. Laboratory compliance, including identity testing and analytical method protocols are now required for any manufacturer, packager, labeler or holder of dietary supplements without the previous exemption based on number of full time employees within the company. Smaller companies, typically without in-house laboratory and testing facilities, now need to obtain such services to meet the new compliance rules.

Process NMR Associates (PNA), the process analytical consulting company and analytical testing company with over 45 years of experience in the field of nuclear magnetic resonance spectroscopy (“NMR”) and organic spectroscopy (FTIR, NIR, ESR) is now offering expanded services for DS GCMP Rule compliance. As an example, The International Aloe Science Council (IASC), a trade association representing the global aloe vera industry, has selected Process NMR Associates, LLC (PNA) as its primary provider for Nuclear Magnetic Resonance (NMR) spectroscopic measurement of aloe vera. PNA’s services include measurement of aloe vera concentration, sacharride distributions, formulation ingredients, and, contaminant/degradation products, in aloe vera powders, whole leaf extracts, whole leaf and inner leaf gel concentrates, drink concentrates, and, ready to drink formulations. PNA’s NMR services are an integral part of the IASC certification and compliance program. “We are pleased to partner with Process-NMR Associates for providing analytical services related to the certification program,” said Devon Powell, Executive Director of the IASC. “PNA has demonstrated its capability to provide excellent analytical services in a timely manner to the organization and aloe vera industry at-large.”

Expanding analyses and methodologies beyond aloe vera include essential oil analyses, fish oils and omega-3 fatty acid analyses, herbal supplement characterization, adulteration monitoring, and, ingredient integrity analyses. It is PNA’s commitment to quality analytical services, sample analysis, reporting turnaround, and competitive pricing that enable us to provide value-added services to the dietary supplement market place.

60 MHz NMR of Essential Oils from Benchtop System – Comparison to 300 MHz NMR Data

A comparison of the non-spinning 60 MHz NMR data compared with that obtained on a superconducting 300 MHz system are shown below for 10 Essential Oils – those essential oils are: Copaibo Balsam, Dill Weed, Citronella, Parsely Seed, Cinnamon Leaf, Balsam (Peru), Ginger, Eucalyptus Globulus, Petitgrain, Vetiver.

Copaibo Balsam NMR Analysis
Dill Weed Essential Oil - NMR Analysis
Citronella Essential Oil - NMR Analysis
Parsley Seed Essential Oil - NMR Analysis
Cinnamon Leaf Essential Oil - NMR Analysis
Balsam - Peru - Essential Oil - NMR Analysis
Eucalyptus Globulus - NMR Analysis
Ginger Essential Oil - NMR Analysis
Petitgrain Essential Oil - NMR Analysis
Vetiver Essential Oil - NMR Analysis

We currently have a database of 1H (60 and 300 MHz) and 13C NMR data of around 110 essential oils.

For further details on NMR analysis of essential oils please contact John Edwards

Solid-State 13C NMR Analysis of Herbal Supplements

Solid-state 13C NMR is an excellent way to investigate what chemical functionality is present in herbal supplements. The large resonances at 60-105 ppm are due to cellulose/polysaccharides and some sugars. The peaks in the 0-60 ppm region are aliphatic carbons in fatty acid chains. Peaks in the 110-140 ppm region are alkene and aromatic carbons, while peaks in the 140 ppm and 150 ppm region are due to substituted aromatics and phenolic carbons. Peaks in the 160-200 ppm region are due to carboxylic acids, esters and amides. Solid-state NMR is a relatively simple technique that involves no sample preparation and observes the sample carbon chemistry in it’s entirety. The analysis reveals relative amounts of chemical functionality that can be utilized for product-to-product comparison or batch-to-batch manufacturing comparison. The chemical specificity of the technique also means that adulterants can readily be detected and identified. A few examples of “off the shelf” herbal supplements are shown below.

Solids 13C NMR of Green Tea - Cranberry - Milk Thistle

Figure 1: 13C CP-MAS NMR of Cranberry Extract, Green Tea Extract, and Milk Thistle Extract

Solids 13C NMR - Bilberry - Echinecea - Black Cohosh

Figure 2: 13C CP-MAS NMR of Black Cohosh Root Extract, Echinecea Powder, and Bilberry Extract

13C NMR of Valerian Ginseng Saw Palmetto, St Johns Wort

Figure 3: 13C CP-MAS NMR of Valerian Root Extract, Ginseng Extract, Saw Palmetto Extract, Grape Seed, and St John’s Wort.

For further details on these analyses and their utilization in quality control contact John Edwards

Benchtop Permanent Magnet High Resolution NMR Systems

The latest buzz in the NMR news release world has been the emergence of the 45 MHz picoSpin (www.picospin.com) miniature NMR system that boasts shoe box size dimensions, a resolution of 80 ppb (3.5 Hz at peak half height), and a tiny 300 micron probe dimension. The sample can be injected with a syringe or pump. A number of application examples and spectra are posted on the application pages of the company website. It is noted that the spectra require the signal averaging of 24-200 pulses requiring an estimated experimental time of 3-10 minutes

The system claims to be the first miniature NMR system but I guess that depends on how you define “miniature”. A number of “relatively small” high resolution permanent magnet NMR systems operating at 60 MHz have been around since the early ’90s (Elbit-ATI, FoxboroNMR, Qualion, ASPeCT-MR, and ACT). The picoSpin NMR is definitely the first spectrometer to deliver high resolution NMR from such a small footprint permanent magnet combined with a capillary probe. The S/N of the picoSpin system is approximately 300:1 on a one pulse spectrum of water. On our 60 MHz systems we are routinely obtaining, non-spinning, one pulse spectra without signal apodization with a S/N of 1600:1 for a 5 mm sample size, and 3600:1 for a 10 mm sample size. Very little degradation of spectrum quality is observed moving from 5-10 mm probe systems. The 5mm lineshape spec is typically LW(50%)=2 Hz (34 ppb), LW(10%)=6 Hz, LW(0.5%)=20 Hz. For the 10 mm probe the spec is typically LW(50%)=2.5 Hz (43 ppb), LW(10%)=13 Hz, LW(0.5%)=80 Hz. We have many example spectra posted on this blog and on our website.

The S/N obtained with 5mm and 10mm sample dimensions represent a 28 and 144 fold improvement of sensitivity compared to the S/N obtained on the picoSpin system. This is a vitally important difference between these two technologies. One yields a useful, repeatable spectrum at a high S/N level after every pulse (4-5 seconds between spectra) while the other requires 100x longer time frame to obtain the same result. In the realm of reaction monitoring this time difference is a huge factor as a reaction can be at completion in a few minutes but an NMR analyzer providing a spectrum every 5 seconds allows dozens of observations to be performed in a short 2 minute reaction. The larger sample dimension in the 60 MHz systems also has the advantage of allowing a much wider range of industrial sector samples to be analyzed with respect to sample viscosity, contamination levels, sample temperature, and “particulate content”.

The picoSpin spectrometer does have a wonderful and truly portable package and will find many applications in university general chemistry labs and in QA/QC of liquid products, but I am not sure that it will have the stability and high sensitivity to allow it’s use in real time process control and reaction monitoring where the samples are complex mixtures, at high temperature, often with particulates present. Also the small probe dimension will mean that the analysis of flowing samples will be extremely difficult because of the small sample volume being analyzed.

Process NMR Associates is currently investigating the possibility of reducing the foot print of their 60 MHz NMR system to a platform that would support a 5 mm sample dimension operating at 60-80 MHz. The magnet would be closer to 50 lbs in weight in this scenario, and with a small FPGA based spectrometer would be a powerful mobile NMR system. However, I do not have a feel for whether the NMR and broader analytical community will be willing to accept the idea of low priced NMR systems selling in the $20-70K range. The question remains….if you build it, will they come? I would be interested to hear any comments on the utility of NMR in the field based on permanent magnet technologies at NMR frequencies of 45-80 MHz. Please address any comments to John Edwards.

IFPAC Conference: Process NMR Associates and University of California, Davis to Present Process NMR and MRI Short Course Prior to Meeting

Short Course on Process NMR and MRI to be presented at the IFPAC Meeting (http://www.ifpac.com/)
When: Monday, January17, 1:00pm to 5:00pm, and continues on Tuesday January 18, 8:00AM to 12 noon
Location: Baltimore Marriott Waterfront
Instructors: Michael J. McCarthy, Professor of Engineering, University of California, Davis, CA
Paul J. Giammatteo, Ph.D., Process NMR Associates LLC, Danbury, CT

The course is specifically designed and organized for industry professionals who want to add to their knowledge-base on magnetic resonance and process analytical technology. Topics include compositional analysis, rheological characterization, measurement of the state of mixing, visualizing transport and product stability as well as recent advances in process magnetic resonance sensors. This course will bring you up-to-date on the latest information concerning the applications and state-of-the art instrumentation for process magnetic resonance.
Outline:
* Introduction to Process NMR Magnetic resonance theory
– Time-domain, High resolution, Diffusion, Imaging
* Hardware
– Spectrometers, magnets, probes
* Coupling the sensor to the process
* Applications will include:
– Composition measurement
– Property measurement
– Rheology measurement
– Product structure
For Details contact Paul Giammatteo Tel: (203) 744-5905 or Michael McCarthy Tel: (530) 752 8921

Press Release: IASC Chooses Process NMR Associates to Provide Analytical Services for Certification Program

The International Aloe Science Council (IASC), a trade association representing the global aloe vera industry, has selected Process NMR Associates, LLC (PNA) as its primary provider for Nuclear Magnetic Resonance (NMR) spectroscopic measurement of aloe vera in regards to the organizations seal-based certification program. PNA’s services include measurement of aloe vera concentration, sacharride distributions, formulation ingredients, and, contaminant/degradation products, in aloe vera powders, whole leaf extracts, whole leaf and inner leaf gel concentrates, drink concentrates, and, ready to drink
formulations.

The IASC certification program, which offers manufacturers the ability to place a seal on products demonstrating that it meets the established standards for quality and purity of aloe vera products available in the marketplace, has elected to use quantitative 1H NMR analysis as a means to determine compliance. “We are pleased to partner with Process-NMR Associates for providing analytical services related to the certification program,” said Devon Powell, Executive Director of the IASC. “PNA has demonstrated its capability to provide excellent analytical services in a timely manner to the organization and aloe vera
industry at-large.”

PNA performs the NMR methodology prescribed by IASC, quantifying constituents such as acemannan, and glucose, identifying breakdown products such as acetic acid, lactic acid, pyruvic and succinic acid, and verifying formulation/preservative additives such as citric and benzoic acids. Adulterants such as maltodextrin can be readily quantified and the presence of non-aloe vera products can also be determined.“Process NMR Associates is proud to have been chosen as a partner for IASC’s certification program needs,” said John Edwards, PNA Manager. “Our commitment to quality analytical services, sample analysis, reporting turnaround, and competitive pricing enable us to provide value-added services to IASC
and others in the aloe vera marketplace.”

The International Aloe Science Council (IASC) is the global trade association dedicated to serving the needs of the aloe vera industry, with a mission to advance, promote and represent the aloe vera industry by providing educational, scientific and self-regulatory leadership and guidance. Membership information can be found at www.iasc.org. Contact: Devon Powell, Executive Director 301.588.2420 x102 (dpowell@iasc.org)

Established in 1997 PNA is a process analytical consulting company and analytical testing laboratory with over 45 years of experience in the field of nuclear magnetic resonance spectroscopy (“NMR”) and organic spectroscopy (FTIR, NIR, ESR). PNA operates high field analytical NMR laboratory for liquid and solid state multinuclear and multi-dimensional NMR analyses. PNA also has several permanent magnet NMR systems that are utilized for laboratory, at-line, and, process FT-NMR and TD-NMR applications. The lab also includes an ATR-FTIR spectrometer, a micro-ESR spectrometer and a Simulated Distillation Gas Chromatograph. Consultation services for analytical technology and application development, development of new instrument platforms and integrate NMR technology with other analytical techniques are also provided. (www.process-nmr.com) Contact: John C. Edwards, Manager, Analytical and Process NMR (john@process-nmr.com)

Process NMR Associates to Present at 3 Meetings

I will be presenting a poster and two invited talks at three meetings this Summer and Fall. The first meeting is Petrophase XI 2010 (11th International Conference on Petroleum Phase Behaviour and Fouling) in Jersey City, NJ, June 13-17 – my poster is entitled: “Improved Approach to the Calculation of Average Molecular Descriptions of Heavy Petroleum Hydrocarbons by Combined Analysis by Quantitative 13C and DEPT-45 NMR Experiments”. The poster describes a new methodology for 13C NMR analysis of heavy petroleum materials based on quantitative 13C and DEPT experiments which can be used in combination to calculate an average aromatic cluster size that is consistent with other analysis techniques. Published approaches being used currently underestimate the size of the aromatic groups in heavy petroleum materials.

In July I will be presenting an invited talk: “A Self-Employed Application Chemists Odyssey in the World of Analytical Instrument Development The Viability of a $50K High Resolution NMR and $15K ESR Spectrometers”, at the University of South Dakota, Vermillion, SD. The date has yet to be set.

I will be presenting an invited talk in a session on reaction monitoring with NMR at SMASH 2010 in Portland Oregon, September 26-29 – my talk is entitled: “Simple and Continuous Flow Reaction Monitoring by High Resolution Bench-top Permanent Magnet 1H NMR at 60 MHz”, by John C. Edwards, Paul J. Giammatteo, at SMASH 2010, in Portland, Oregon.

Process NMR Associates – Journal Article Published

An article by Dr. John Edwards of Process NMR Associates and researchers at the Southern Regional Research Center of the US Department of Agriculture (Dr. H.N. Cheng, Lynda H. Wartelle, K. Thomas Klasson) has been accepted for publication in the Elsevier Journal Carbon. The paper entitled “Solid state NMR and ESR studies of activated carbons produced from pecan shells” is available at the following link: Carbon Paper . Process NMR Associates provided the solid-state 13C NMR, TD-NMR, and ESR spectroscopy for the analysis of the activated carbons derived from pecan shells.

Permanent Magnet Based NMR for Omega-3 Fatty Acid Analysis

We are currently developing a spinner system for the process NMR system in order to improve spectral resolution sufficiently to quantify omega-3 fatty acids in fish oils. The omega-3 fatty acid methyl group can be discerned in the 1H spectra currently produced by the spectrometer but improvement can be made with sample spinning which will improve the quantitation.

Fish Oil Omega-3 by 1H NMR

Fish Oil Omega-3 Fatty Acids by 1H NMR

Solid-State 13C NMR of Kitchen Herbs

Kitchen Herbs by Solids 13C NMR - 1

Kitchen Herbs by Solids 13C NMR - 2

NMR Post-Processing Freeware

It was announced this week that the ACD NMR Processor Academic Edition is freely available for non-commercial use and can be downloaded from the ACD Website. Other Windows based NMR processing software packages are available and here is a listing of where they can be downloaded:

1) SpinWorks – written by Kirk Marat at the University of Manitoba – Download Here

2) GSim – written by Vadim Zorin Download Here

3) RNMR (Requires R Statistical Freeware Package) – Download HereR Software can be obtained here

4) MatNMR (Requires MATLAB) – Download Here

5) Hires – Download Here

 

Process NMR Spectroscopy Chapter to Appear in Wiley Publication

John Edwards and Paul Giammatteo of Process NMR Associates have written a chapter “Process NMR Spectroscopy: Technology and On-Line Applications” to appear in the 2nd Edition of “Process Analytical Technology” published by Wiley and Sons and Edited by Katherine Bakeev. The book will be published in May 2010 and is available for pre-order.

Process Analytical Technology - 2nd Ed. - Wiley


Digital Spectrometers Will Change the Marketplace for NMR Technology

Digital Spectrometers based on field programmable gate arrays will soon change the face of NMR spectroscopy as a routine use analytical instrument. Stan Sykora in his excellent blog (http://www.ebyte.it/stan/blog07.html#07jun14) describes how the transition of NMR spectrometers to digital electronics has drastically reduced the footprint and price of NMR spectrometers and increased the potential complexity of the RF synthesis as well as the NMR post processing on the same chip. In fact single chips can hold multiple spectrometers enabling the building of single spectrometers that can perform experiments on multiple magnet systems.

One of the best journal articles on the topic is by Kazuyuki Takeda “OPENCORE NMR: Open-source core modules for implementing an integrated FPGA-based NMR spectrometer”, Journal of Magnetic Resonance, 192(2), 218-229, 2008. This gentleman also included all the core modules, console software, pulse programs and board designs required to build your own spectrometer (see Opencore Website). The availability of superconducting NMR magnets are still the barrier to entry for cheaper high field NMR systems but in the lower field NMR area these spectrometers will enable a drastic reduction in instrumentation cost and perhaps lead to a larger NMR market. In the near future I feel that NMR systems in the 200/300 MHz range will be quite affordable especially if the consoles are married to older magnets that are currently gathering dust in rear storage areas.

The appearance of Bruker’s Fourier 300 NMR spectrometer bears witness to the market that is there for a company that can deliver a well priced NMR instrument in combination with strong application software. In fact I think that these cheaper spectrometers will facilitate the development of a market where NMR instrumentation will be sold to address individual analytical problems in routine testing laboratories. Perhaps NMR standard methods will become as prevalent as GC and MS methods currently are. Imagine an NMR spectrometer sold to a laboratory not as a general research tool but as a dedicated instrument performing authentification testing on olive oils sold in the EU. This is a new concept for NMR chemists to wrap their heads around….smaller, cheaper NMR instruments driven by applications rather than magnetic field strength.

2 x FPGA 
Spectrometer Design

A two FPGA spectrometer design is illustrated in the two figures.

FPGA1 NMR 
Component Details

Process NMR Under Continuous Flow

The use of an NMR as a simple flow detector for benchtop reaction monitoring, mixing monitoring, dilution monitoring, or conversion monitoring has been limited by the need to bring the “reaction” to the typical “supercon” NMR lab. We are introducing a continuous flow NMR system that can be on the benchtop. The system uses a high resolution 60 MHz permanent magnet with a simple flow cell and total system volumes of 2 to 5 ml depending on the length and diameter of the transfer tubing. Further, detection limits of analytes in the 200+ ppm range are possible without the use of typical deuterated NMR solvents. Analysis times of 5 to 20 seconds are also possible at flow rates of 5 to 20+ ml/minute.

NMR Probe 
Insert for Flow NMR

As an example, we observed the Hydrogen bonding exchange rate between the OH protons on isopropyl alcohol with the hydrogen of water as a function of increasing water concentration. Figure 1 shows the starting spectrum (blue) of “of the shelf” 91 vol % IPA obtained at the local pharmacy flowing through the NMR at 10 ml/min. At this concentration, the IPA OH hydrogen and water hydrogen are spectrally distinct. The red spectrum is the final spectrum after 50 minutes of slowing adding water to the original IPA to bring the IPA concentration to approximately 76 vol %. At the end of the dilution, the OH peaks from IPA and water are in complete exchange as represented by the single peak.

Water Added to
 Isopropyl Alcohol 1


Water Added to 
Isopropyl Alcohol 2


Figure 1: “Off the Shelf” Isopropyl Alcohol at the original concentration of 91 vol % IPA (blue) and diluted to 76 vol % (red).

Figure 2 shows the results of the sequential addition of 20 0.5 ml aliquots of water that take the original 91% IPA to its final concentration of 76%. As shown in Figure 3, one can readily observe the convergence of the OH peaks as the dilution progresses.

Water in 
Isopropyl Alcohol - NMR Progression


Figure 2. Continuous flow NMR dilution monitoring of 91% by volume isopropyl alcohol with water to a final concentration of 76%.

Water in 
Isopropyl Alcohol - NMR Progression 2
Figure 3.

Continuous flow NMR monitoring of OH hydrogen exchange between water and isopropyl alcohol as a function of IPA concentration.

Continuous Flow NMR was also used to monitor solute addition in a non-mixed vessel. In this experiment a concentrated table sugar solution (2.19 molar) was injected every 100 seconds at an injection volume of 0.083 ml each for the first 30 minutes (1 ml total) with two final injections of 0.5 ml each. Starting volume of water was 25 ml. Total volume of sugar solution injected was 2.0 ml representing 1.5 grams of table sugar. Flow rate through the NMR flow cell was 10 ml/min with a total NMR sample volume (tubing + flow cell) was 5 ml. Again, no solvent suppression was applied.

Figure 4 shows the overall spectra through the entire run. Figure 5 shows the expansion of the water/carbohydrate region showing the sensitivity of the 60 MHz flow NMR to sugar concentration.

Sugar in Water
 - NMR Analysis 1


Figure 4. Overall flow NMR results for concentrated sugar solution addition to water.

Sugar in Water
 - NMR Analysis 2


Figure 5. Water/carbohydrate region expansion showing table sugar addition to water.

 

Reaction Monitoring by Process NMR

Simple Reaction Chemistry

Presented here are several simple reactions monitored by 60 MHz process NMR performed in a 5 mm NMR tube.

Reaction #1: Acetic Anhydride in Water – Reacts to form Acetic Acid

Acetic Anhydride
 in Water - Reaction Monitored by process NMR

Reaction #2: Acetic Anhydride + Excess of Methanol + Acid – Yields Acetic Acid and Acetic Methyl Ester

First Reaction was Performed without Shaking the Sample before Observation

Acetic Anhydride
 in Methanol - Acid Catalyzed - 1H NMR

 

 

Reaction 
Monitrong by NMR - AA+Methanol

Second Reaction was Performed with a vigorous shake of the NMR tube before observation.

AA+MeOH - Shaken
 - 1H NMR

AA+MeOH Shaken -
 1H NMR - Zoom

NMR Reaction 
Monitoring - AA in MeOH - 1H NMR

For More Information Contact John Edwards


Examples of 60 MHz Process NMR Spectral Resolution

These are non-spinning spectra obtained on a Qualion process NMR spectrometer operating at 58 MHz. The spec on water at this shim level is 1.5/5/20 Hz at 50%/10%/0.5% peak height. The first spectrum is of 91% isopropyl alcohol in water – store bought pharmacy product. The second spectrum shows the comparison of a 300 MHz 1H NMR spectrum of Advil compared to a non-spinning 58 MHz spectrum.

91% Isopropyl Alcohol in Water - 1H NMR

Comparison of 
300 and 58 MHz 1H NMR of Advil

 

A Self-Employed Application Chemists Odyssey in the World of Analytical Instrument Development: The Viability of a $50K High Resolution NMR and $15K ESR Spectrometers

Presented at Marist College, Poughkeepsie
September 23, 2009

A Self-Employed Application Chemists Odyssey in the World of Analytical Instrument Development The Viability of a $50K High Resolution NMR and $15K ESR Spectrometers

By John C. Edwards, Ph.D.
Process NMR Associates, LLC, Danbury CT

The availability of cheap commodity electronics developed for the cellular phone industry is revolutionizing the design of NMR and ESR spectrometers. Rather than instruments that fill half a room, cost $200-3,000K+, and intimidate users, it is possible to produce spectrometers that are an order of magnitude cheaper to produce. Examples of NMR and ESR spectrometer development projects will be described as well as the wide-ranging applications that these spectrometers can deliver to the areas or process control, food authentification and automated laboratory analysis.

Bio:

John Edwards was born and raised in Bolton, UK. He graduated from the University of Durham, UK with a B.Sc. in Chemistry in 1986. He obtained his Ph.D. in Physical Chemistry from the University of South Carolina in 1990, working on solid-state NMR applied to heterogeneous catalysts under the guidance of Professor Paul Ellis. From 1990-1997 he worked as a research chemist at the Texaco R&D facilityin Beacon, NY where he was responsible for global NMR support of upstream, downstream, and petrochemical Texaco ventures. In 1997 he formed Process NMR Associates which operates as a commercial analytical NMR spectroscopy service and consultancy. Process NMR Associates along with its engineering company partners, develops, markets, and supports on-line process NMR spectrometers utilized for control and optimization of refinery, petrochemical, pharmaceutical and food manufacturing operations. The company also acts as an application development company for several analytical instrument companies and supports the chemometric development of several process analytical products. He currently resides in Poughkeepsie, NY, with his wife and 3 sons. He is an affiliate professor of Chemistry at Marist College, a Research Associate at SUNY New Paltz, and an active member of the American Chemical Society.

A copy of the presentation can be provided on request… contact John Edwards if interested.

News: Process NMR Associates and TopNIR Sign Partnership Agreement

Topnir Systems is proud to announce the signature in October 2009 of a Partnership Agreement with Process NMR Associates, LLC.

This partnership enables Process NMR to utilize our field proven software in complementary fields NMR and MIR combining forces to deliver total solutions with increased added value to customers.

Topnir Systems is a French company leader in the field of online Near InfraRed (NIR) analyzers. Topnir enables measuring and monitoring multiple hydrocarbon streams in less than one minute using a single online system. The company has a long history in the refining and petrochemicals business, being the first world wide to implement an online application designed to measure and control octane number for gasoline production, first NIR on-line application worldwide on Ethylene Plant Naphtha feed (1986), Gasoline (1989) and Crude (1991). The business started in the late 80s within BP Oil, with applications development around gasoline and diesel blending, as well as FCC, CDU, Reformer and Ethylene plant feed andproducts characterization. Major oil companies such as Shell, BP, Repsol, Aramco… have adopted Topnir solutions.

Topnir has recently expanded its activities to provide platform independent software for NIR systems already installed in the field. Topnirs modeling technology offers a full set of properties from a single model which offers the advantage of a robust, reliable system requiring very light maintenance. In addition Topnir is field proven to have ASTM and better results.

Process NMR Associates, LLC is an American company and leader in the field of online Nuclear Magnetic Resonance (NMR) process applications. The company also has a long history in the refining and petrochemicals business, being the first world wide to implement online NMR applications for gasoline and diesel blending, FCC, CDU, Reformer and Ethylene plant feed and products characterization.

Topnir Systems SAS
425, rue RenéDescartes
Espace Descartes, Bat C
Parc de la Duranne
13857 Aix-en-Provence, France
Tel +3350 73 47 / Fax+3350 73 50
Web: www.topnir..com
USA Contact: Julie Williams Tel: +1-508-736-2696

Process NMR Associates, LLC
87A Sand Pit Road
Danbury, Connecticut 06810 USA
Tel +203-744-5905
Fax +203-743-9297
Web: www.process-nmr.com
Contact: Dr. Paul Giammatteo


PNA Presentations at 104th Gulf Coast Conference

Paul Giammatteo recently presented two papers at the Gulf Coast conference that was held in Galveston, Texas on January 20-21.

His first paper was entitled “Counting Carbons for Tighter Control: Combining GC and NMR to Improve Distillate Manufacturing” and centers on the topics of Simulated distillation correlated to 1H NMR.

The second paper was entitled “Analytical Data For Engineering Support: Improving the Lab/Process Interface”. This paper details the development of a series of heavy petroleum applications on a Smiths Detection FTIR-ATR spectrometer.

PDFs of the presentations can be obtained from the following links: 1) NMR Talk 2) FTIR-ATR Talk


ASTM F2259-03 (2008) – Determining the Chemical Composition and Sequence in Alginate by 1H NMR

Alginate is a linear polysaccharide composed of mannuronate (M) and a-L-guluronate (G). The polysaccharide is characterized by the relative ratio of M/G, G-Content, and average length of blocks of G in the polymer. M and G are:

ASTM F2259 recounts the standard sample preparation and 1H NMR analysis that allows the following parameters to be calculated:

 

The 1H Spectra obtained on a typical alginate sample are show below:

 

 


 

Finally the peaks representing the individual M and G components and sequences are deconvoluted from the spectrum.
The intensities obtained from the deconvolution are input into the excel spreadsheet shown above and the various ratios, M and G content and a series of diads and triads are calculated along with some G block length information. It is the block length information that often reveals telling differences between samples.

Process NMR Associates performs this analysis at a cost of $225 per sample. The samples, however, must be prepared by the customer using the methodologt set forth in the test method.


NMR Analysis of Vinegar for Authentification and

Detection of Adulteration

Over the past few years balsamic vinegars have been the subject of a number or NMR studies to determine authenticity, degree of aduleration, and age. 1H NMR has been used to quantify the relative concentrations of a series of organic components (ethanol, fructose, glucose, acetic acid, succinic acid, lactic acid, butandiol, etc (ref 1). 13C NMR has been used to determine the aunthenticity and degree of adulteration (ref 2) as well as the length of the ageing process that a given sample has undergone. Also the formation of glucose and fructose acetates during maturation and ageing has been studied by 1H and 13C NMR.

Refs.
1) Caligiani et al., Anal. Chim. Acta, 585 (2007) 110-119
2) Consonni et al., Talanta, 75 (2008) 765-769
3) Consonni et al., Anal. Chim. Acta, 611 (2008) 31-40
4) Consonni and Caligiani, Talanta, 73 (2007) 332-339
5) Cirlini et al, Food Chemistry, 112 (2009) 51-56

The concentration and distribution of the organic components has been found to correlate well with ageing process analysis, identification of adulteration, and determination of authenticity of traditional balsamic vinegars and balsamic vinegars of Modena.
Below are a series of spectra showing what can chemistry can be quantified in the balsamic vinegars as well as a few comparative spectra of apple cider vinegar and malt vinegar.









NMR Analysis of Commercial Pear Cider

For comparison with the home made ciders analyzed in the previous posting I am including the NMR of analysis of a commercial pear cider. The previous ciders were very dry while the pear cider was decidedly sweet. The carbohydrate content is a notable difference. The 1H spectrum is shown with chemical components identified.


 

October 31, 2008

1H NMR Analysis of Hard Apple Cider

Filed under: NMR — processn @ 4:18 pm

There have been quite a lot of NMR studies centered around apple cider (non-alcoholic) and apple cider vinegar. However a search of the literature turns up no reference for NMR analysis of hard apple cider. This effort was undertaken to analyse the alcohol content of the ciders and to determine the malic and acetic acid content. Ciders were produced by Dr Tim McMahon of Orange Community College, NY….for his own consumption.

Below are the NMR spectra obtained by regular 1H acquisition and with BINOM solvent suppression.

Data was obtained on our Varian 300 MHz spectrometer. Samples were prepared by degassing followed by addition of 1 drop of D2O as lock solvent.

Hard Cider #1 - NMR Analysis - Full Spectrum

Hard Cider #1 - NMR Analysis - Full Spectrum

Hard Cider #1 - NMR Analysis - Full Spectrum

 

Micro-ESR Spectrometry of Crude Oils

Filed under: NMR — processn @ 3:36 pm

Process NMR Associates, LLC (Danbury CT) and Active Spectrum, Inc (San Carlos CA) are collaborating in the application of micro-ESR technology to petroleum applications. The initial work has focussed on crude oils but will soon be expanded to residues and cracker feedstocks.

Five samples of crude oil were tested by Micro-ESR spectrometry. The samples were:

1. Vasconia, Magdalena Basin, Columbia (V=39 ppm)
2. Merey, Eastern Venezuela Basin, Venezuela (V=303 ppm)
3. Oriente, Oriente Basin, Ecuador (V=65 ppm)
4. Qua Iboe, Agbada Formation, Niger Delta (V=2 ppm)
5. Basrah Light, Zubair Zone, Iraq (V=29 ppm)

The following spectra were observed:

Micro-ESR Spectra of Crude Oils

Figure 1: Micro-ESR Spectra of Crude Oil

The central peak is a combination of a persistent carbon-centered organic radical (g = 2.003) found in asphaltenes, and a vanadyl (VO2+) peak. The additional smaller peaks are associated with vanadyl only.

For producers, the technique could be used to rapidly measure asphaltene concentration on-line. The spin density of the organic radical is a function of the maturity of the oil and will of course vary between deposits. Notwithstanding, rapid electronic measurement of asphaltenes remains a topic of great interest. Similar techniques have also been used to assess the quality of coals. For refiners, vanadium is a contaminant that poisons the refinery catalyst. ESR has been used by refiners since 1962 to rapidly measure vanadium content in crude oil feedstocks both on-line and in laboratories. Active Spectrum Inc.’s Micro-ESR is shown below. It is 2.25″ in diameter by 2.5″ high. Power input is 12-30VDC, and the data interface is USB. The device is available as either an on-line sensor or as a benchtop unit.

Micro-ESR Probe/Magnet Assembly

Figure 2: Micro-ESR Sensor

Higher resolution ESR spectrum of Merey Crude Oil

Figure 3: Higher Homogeneity Spectrum of Merey Crude

Micro-ESR is complimentary to NMR in that it observes paramagnetic metals and organic radicals which are unobservable by NMR. The stable free radical signal is indicative and quantitative to the amount of asphaltenes in the crude oil sample and vanadium metal content is an important processing parameter for cracking processes as it is active in the passivation of catalysts. NMR on the other hand observed the detailed hydrocarbon chemistry of the sample and yields chemico-physical parameters such as aromaticity, paraffinicity, naphthenicity, distillation, density, PAH distribution. In combination these two technologies yield a detailed picture of the petroleum materials before and during the refining process.

Samples provided by John Edwards of Process NMR Associates, LLC. Micro-ESR analysis provided by James White of Active Spectrum, Inc,

Active Spectrum Inc Logo
Active Spectrum, Inc. 110 Glenn Way #15, San Carlos, CA 94070 650-610-0720 | 626-628-1970 f | activespectrum.com

Process NMR Associates, LLC Logo
Process NMR Associates, LLC. 87A Sand Pit Rd, Danbury, CT 06810 203-744-5905 | 203-743-9297 f | process-nmr.com

PDF Version of Application Note

For more information contact John Edwards (203) 744-5905

Residual Catalytic Cracking (RCC) - Feedstream Analysis by NMR

Filed under: NMR — processn @ 10:32 am

Current Technique for Feedstream Analysis:
Analysis Performed – Refractive Index, Distillation, Specific Gravity
Calculation Obtained – Watson K-Factor
Outcome: aromatic carbon number, aromatic hydrogen number, total hydrogen content
Proposition: Detailed hydrocarbon analysis for kinetic model development.

Our experience is that an improved and useful analysis can be obtained from NMR
analysis. There are several ways to approach the NMR analysis and the
chemometric approach to correlating NMR data to physico-chemical parameters of
use to process control.

RCC Feedstream Analysis by 1H and 13C NMR: Multivariate Prediction of Chemical and Physical Properties

Presented at the 236th ACS National Meeting, Philadelphia PA, August 17-21, 2008

John C. Edwards Ph.D.
Process NMR Associates LLC
87A Sand Pit Rd, Danbury, CT 06810

Jincheol Kim,
SK Energy Co., Ltd, SK Energy Technology Center,
140-1, Wonchon-dong, Yuseong-gu, Daejeon 305-712, Korea

Summary of Slides

1) 60 MHz process NMR data available from online NMR unit.

60 MHz Process NMR Data available from online NMR Unit

2) 300 MHz 1H NMR data available from standard NMR experiments on laboratory NMR system at Process NMR Associates

300 MHz 1H NMR Data - RCC Feeds

3) Expansions of 1H NMR data on RCC Feeds

Expansion of 300 MHz 1H NMR Data - RCC Feeds

4) Calculated 1H NMR Parameters Represented as an alternative “spectrum” for use in chemometric modeling and linear regression.

Calculated 1H NMR Parameters Represented as a

5) 13C NMR Data obtained on RCC Feeds

13C NMR Data  - RCC feeds

6) Expansions of 13C NMR Data

Expansions of 13C NMR Data - RCC Feeds

7) 13C NMR and Average Molecule Parameters Calculated from 13C Spectrum

13C NMR - Calculated Parameters

8) Calculated 13C NMR Parameters Represented as an alternative “spectrum” for use in chemometric modeling and linear regression.

13C NMR Parameters Represented as a

9) Correlations of Spectra and Calculated Parameters to Physico-Chemical properties of RCC Feeds

Correlations of Spectra and Calculated Parameters to Physico-Chemical Properties of RCC Feed

10) Correlation of Spectra and Calculated Parameters to Density

Correlation of Spectra and Calculated parameters with Density

11) Variable Selection for Linear Correlation of Calculated NMR Parameters to Physico-Chemical Properties of RCC Feeds.

Variable Selection for Linear Correlations

12) Correlation of Calculated 13C NMR Parameters (C-Type and Average Molecule) with both high resolution 1H and 13C NMR spectra. Models created can be utilized by personnel with no NMR experience to calculate NMR parameters directly from the spectrum without any prior knowledge of integrations or calculations to be performed.

Correlation of 1H and 13C NMR Spectra with Calculated 13C NMR Parameters

Summary
Chemical and Physical Properties of RCC Feedstreams can be determined
by 1H NMR (at 60 and 300 MHz) and by 13C NMR
H-Type and C-Type Parameters do not provide as good a correlation as is observed
by full spectrum regression. This is due to loss of resolved chemical shift information
when the spectrum is reduced to larger integral areas.
1H NMR can be combined with PLS regression modeling to provide detailed carbon
type analysis for RCC Feeds
Regression analysis of 13C NMR data can be utilized to fully automate the prediction
of 13C NMR type analysis : reducing the necessity for considerable knowledge and
analysis time on the part of the analyst.

For further Detail Contact John Edwards

 

Diesel Production Control - Combination of NMR and Simulated Distillation to Yield On-Line Carbon Number Distributions

Process NMR Associates has developed a database of Simulated Distillation database on a large number of diesel fuels on our Shimadzu 2010-GC with SimDis Software. The analysis is being used to develop distillation prediction models for the process NMR systems as well as explore new avenues of control information that can be derived by combining carbon number distributions obtained from the GC data with the predictive capabilities of online NMR.

For a PDF version of this application article download this: Combination of NMR and Simulated Distillation for Diesel Production Control

Simulated distillation allows carbon number distributions to be calculated and in combination with chemistry observed in the NMR analysis the effect of aromatics and olefins on the paraffin distributios can be estimated. Online NMR predictions can be established that yield real-time carbon number distributions for production control and sulfur species monitoring.

Contact: Paul Giammatteo at paul@process-nmr.com or +1 (203) 744-5905

 

Extensive NMR Diesel Database Enhances NMR Model Performance for Unit Control and Product Manufacturing
 

An extensive database (10 years) of diesel samples incorporating all refining processes (distillation through product blending) enables development of robust, wide ranging property predictions independent of crude sources and refinery processing.  Consistent attention to data integrity enables expanding model ranges well beyond any typical single unit or process operation.  The following slides elucidate the consistency in spectra whether obtained 10 years ago or last week, from within a refinery or on a laboratory spectrometer.

For a PDF version of this application article download this:  NMR for Diesel Production Control

 

 

If you are interested in discussing the applicability of NMR to diesel production control do not hesitate to contact us at (203) 744-5905 or at paul@process-nmr.com.

September 15, 2008

Quantitative NMR Analysis of Wine - qNMR

Filed under: NMR — processn @ 7:52 am Edit This

Here is an example of a 1H NMR analysis of a 2007 Red Wine submitted for chemical analysis by John W.

1H NMR Spectrum - Quantitative Analysis of Wine

1H NMR of Wine - Detailed Component Breakdown

NMR Analysis - Quantitative Component Calculation

If you are interested in wine analysis please contact us.

Solid-State 13C NMR Analysis of Carbonaceous Materials

Filed under: Energy, NMR — processn @ 6:38 am Edit This

Over the past 20 years we have obtained the solid-state NMR analysis of pretty much every carbonaceous material that exists - including coal/oil shales/bitumen, polymers/catalysts/fibers, cellulose/polysaccharides/foodstuffs/gels, deposits/dried sewage/meteorites/soils/clays, etc. With the increased attention to coal liquifaction and gasification technologies we have developed an interest in creating an NMR database for coals. Coals were obtained from the Penn State Coal Sample Bank at a very reasonable cost. We have performed CP-MAS, DD-MAS, Variable Contact Time, and T1 inversion recovery experiments on all the samples. We are currently developing regression relationships between the NMR data and the physical and chemical testing data that is provided with the samples. At some point we will write this up as a journal article. Here are some snippets of data from the coal analysis along with a few results obtained on the menagerie of samples we look at on any given day including some oil shales, engine deposits, refinery coke, asphaltenes, and pipe tobacco.

Solid-State 13C NMR - Illinois #6 Coal

Solid-State 13C NMR - Hiawatha Coal

Solid-State 13C NMR - Coals: Rosebud and Dietz

Solid-State 13C NMR - Engine Deposits: CCD and IVD

Solid-State 13C NMR - Refinery Coke

Solid-State 13C NMR - Arab Medium Heavy Asphaltene

Solid-State 13C NMR - Pipe Tobacco

Please inquire if you are interested in the details of the above analyses.

September 13, 2008

60 MHz TD-NMR System

Filed under: NMR, TD-NMR — processn @ 9:42 pm Edit This

Process NMR Associates and Spin Resonance Ltd have recently completed the construction a small 60 MHz (1.4T) 5mm TD-NMR system that can be utilized to study T1 and T2 characteristics of novel contrast agents at typical MRI frequencies. Here are a few pictures of the magnet. It is based on N42 neodymium-iron discs (120mm diameter x 30 mm deep).

60 MHz NMR Console - Hahn Echo

60 MHz NMR - CPMG

60 MHz NMR - T1 - 90-90 Experiment

60 MHZ NMR Magnet with 5 mm Probe

60 MHz TD-NMR Magnet

February 28, 2008

Process NMR Application: Spectro-Molecular Control for Enhanced Diesel Recovery

Filed under: Energy, NMR, Process NMR — processn @ 1:18 pm Edit This

NMR Process Systems – Integrated Solution

Application for Crude Unit and Downstream Processes:
Spectro-Molecular Control for Enhanced Diesel Recovery

NMR Process Systems’ (NPS) on-line NMR based analytical and process control strategy for enhanced diesel recovery at the crude distillation unit maximizes clean diesel recovery by enabling closer cut point control in the mid-section of the CDU.

Clean Fuels regulations in both the European and American markets have had a substantial impact on a refiner’s ability to maximize product draws at the refinery front end. Extremely low sulfur requirements for gasoline and diesel have resulted in refiners now being more constrained at the hydrotreaters. Lack of reliable, focused, measurement and control of critical CDU product draws has forced many refiners to significantly undercut these draws in order to ensure minimum error in the final product blends, especially with respect to total sulfur. Depending on a refinery’s crude supply and CDU capacity, a conservative estimate of 300-500+ barrels per day of loss diesel production is typical. With an average of $25-$35 per barrel margin loss, the economic impact of these Clean Fuels Regulations are substantial.

Integrating proven NMR technology with a focused measurement and control strategy enables crude unit operations to cut “chemically” closer to the hydrotreater constraint limit. The strength of NMR is that it quantitatively and accurately “observes” the chemistry of each refinery stream and readily relates that chemistry to chemically dependent parameters such as distillation, cetane, freeze points, etc. The NPS strategy is to cut and control CDU diesel production as closely to the dibenzothiophene distillation limit as possible. Figure 1 illustrates this strategy in terms of both current and proposed NMR based measurements.

Figure 1: Overall NMR measurement and control outline highlighting measurement/control strategies.

Enhanced Diesel Recovery

Let NMR Process Systems deliver “Spectro-Molecular” Control to your refinery so that you can achieve real economic and production benefits.

January 28, 2008

Process NMR Associates - Archives - Gasoline Analysis by NMR and Chemometrics - ENC 1996

Filed under: Chemistry, NIR, NMR, Process NMR — processn @ 8:55 pm Edit This

Just came across an old presentation on gasoline analysis by NMR and chemometrics with direct comparisons to Mid-IR and NIR. Presented at the Experimental NMR Conference in March 1996….PDF (3 MB)

 

Conjugated Diolefins Analysis by COSY NMR

Filed under: Chemistry, NMR — processn @ 8:51 pm Edit This

Conjugated diolefins are responsible for fouling of many processes in a refinery. COSY NMR analysis can determine the concentration of these species in many processed petroleum product streams….see PNA webs site.

Conjugated Olefins by COSY NMR - 1D 1H NMR - Coker Naphtha

Conjugated Olefins by COSY NMR - COSY - Coker Naphtha Showing Conjugated Olefin Signals

Conjugated Olefins by COSY NMR - Hydrotreated Naphtha

Conjugated Olefins by COSY NMR - Hydrotreated Naphtha

October 29, 2007

Schering-Plough Corporation Seeks Process Analytical Technology Manager

Filed under: IR-ATR, NIR, NMR, PAT, Process NMR — processn @ 8:58 pm Edit This

Title:
Process Analytical Technology (PAT) Manager

Description:
Implement Process Analytical Technology (PAT) throughout all the Global Quality Sites to identification of incoming materials and monitor manufacturing processes.
Work directly with the sites and Schering Plough Research Institute to help support / initiate the development, validation, and deployment of PAT at the sites.
Review, evaluate, implement, and manage PAT activities.
Provide guidance / technical help to the sites to conduct evaluation and purchase commercial PAT related analytical equipment (e.g. NIR / FT-NIR, Raman / FT-Raman, IR / FT - IR etc.).
Maintain analytical instruments in the lab to comply with cGMP standards and requirements.
Train and mentor laboratory staff on PAT to generate analytical data for routine experiments.
Generate network and infrastructures with various sites of the corporation.
Take full ownership / responsibility and provide effective, meaningful, result driven and pro-active leadership on all PAT projects.
Responsible to transfer knowledge / technology of PAT related projects and activities to sites. Job is located in New Jersey.

Respectfully, Vincent L. Graziano
Recruiting Manager / Global Staffing
Schering-Plough Corporation
556 Morris Avenue, S1-1
Summit, N.J. 07901
Ph: 908-473-2745
Fx: 908-473-2793
Ph: 908-298-5232 (Kenilworth)
Careers: Employment Opportunities
email: vincent.graziano@spcorp.com 

NPS - IS : A New Approach to Process Analytical

Filed under: Chemistry, Energy, IR-ATR, NIR, NMR, Process NMR, TD-NMR — processn @ 5:34 pm Edit This

Press Release - NMR Process Systems - Swagelok Technology Conference, Teaneck NJ - October 23, 2007

NMR Process Systems, LLC Announces  NPS-IS© -   NPS – Integrated Solutions

NMR Process Systems (NPS) announces a new era in advanced analyzer and process control solutions for on-line and at-line process applications. NPS’s Integrated Solutions (NPS-IS©) approach is designed to take advanced on-line analysis to the next level in delivering real engineering and economic benefit to the user. 

NPS-IS©: the first and original source for any and all on-line NMR applications regardless of NMR vendor.

NPS-IS©: the first to offer integrated advanced analytical solutions using multiple technologies “in one box”.

NPS-IS©: the first to offer a fully integrated Swagelok sampling solution for improved sample switching and reliable measurement.

Too many spectroscopic based on-line analyzer projects (FTIR, NIR, NMR) have failed to meet expectations and/or objectives due to:

·         Overselling the measurement

·         Underestimating the sampling requirements

·         Trying to replace all traditional analyzers with one technique.

NMR Process Systems is positioned to deliver the real benefits of advanced analytical systems in petroleum, petrochemical, chemical, food and beverage and pharmaceutical applications.  Moving beyond the traditional replacement analyzer philosophy, “NPS-IS©” integrating analyzers and advanced controls to deliver real process improvement and economic benefit. Such integration leverages the strength of any individual spectroscopy, shortens per stream analysis time, and builds in internal cross-checking to ensure accuracy.

For more information contact Paul Giammatteo Principal, NMR Process Systems

87A Sand Pit Rd, Danbury, CT 06810 U.S.A.  Tel: (203) 744-5905

The RefinIR - FTIR-ATR Petroleum Product Analyzer

Filed under: Chemistry, IR-ATR, Process NMR — processn @ 5:32 pm Edit This

Press Release - NMR Process Systems - Gulf Coast Conference, Galveston Island, Texas - October 17, 2007

NMR Process Systems, LLC and Smith’s Detection Launch RefinIRTM - The New Refinery Products Analyzer

In a joint development effort NMR Process Systems and Smith’s Detection have developed a range of petroleum analyzer products based on a mid-infrared spectrometer which utilizes an attenuated total reflection (ATR) sample interface. The ATR allows wipe and swipe sample introduction that is ideal for heavy petroleum analysis. Chemometric approaches to chemical and physical property prediction have been developed as well as analysis by spectral database matching. The FTIR-ATR spectrometer is called the RefinIR which can be utilized in the laboratory for rountine, multi-parameter prediction of  petroleum product properties or to aid in process troubleshooting on unusual samples or solid foulants.

For more information contact Paul Giammatteo Principal, NMR Process Systems

87A Sand Pit Rd, Danbury, CT 06810 U.S.A.  Tel: (203) 744-5905

Process NMR Associates Develops Oxford QP-20 Spectrometer Replacement

Filed under: NMR, Process NMR — processn @ 5:29 pm Edit This

In a joint development effort Process NMR Associates and Resonance Systems Ltd have developed a replacement NMR spectrometer for the Oxford QP-20 TD-NMR analyzer. In many cases the excellent magnet and probe of the QP-20 continue to work effectively long after the NMR spectrometer has died. The Spin Track-20 spectrometer enables the user to completely replace the QP-20 NMR system while retaining the use of the original magnet and probe configuration. The product represents state-of-the-art digital NMR technology allowing newly developed TD-NMR methodologies to be applied to complex systems with all the advantages of a windows computer system (replacing the paper cartridge of the original system). Customers who have malfunctioning QP-20 NMR systems can obtain a modern digital NMR system within 8 weeks of order and for less than $16,000. The modular design of the Spin Track TD-NMR systems allows our engineers to develop replacement systems for all benchtop NMR systems such as those marketed by Oxford Instruments, Bruker Minispec, and Resonance Systems. Contact us if you have a non-functioning system that might be a candidate for the Spin Track upgrade.

For more information contact John Edwards Principal, Process NMR Associates - Spin Track Division
87A Sand Pit Rd, Danbury, CT 06810 U.S.A. Tel: (203) 744-5905

 

PNA Presentation at 9th Upstate NY NMR Symposium

State University of New York
College of Environmental Science and Forestry (SUNY-ESF)
Syracuse, NY, 13210
Alumni Lounge– Marshall Hall
October 12, 2007

Co-Organizers

SUNY-ESF Syracuse University SUNY Upstate Medical University Bristol-Myers Squibb
Art Stipanovic Phil Borer Stewart Loh Doug Weaver
Dave Kiemle Stephan Wilkens  

Sponsors

  • SUNY-ESF
  • Syracuse University
  • Bruker Biospin
  • Bristol-Myers Squibb
  • Process NMR Associates LLC
  • Isotec
  • Cambridge Isotope Laboratories
  • Varian Inc.

The 9th annual Upstate NY NMR Symposium will be held at SUNY-ESF on Friday, October 12th featuring keynote speaker Professor Ruth E. Stark, Director Institute for Macromolecular Assemblies, CUNY. Others from around the region will also highlight their work in short presentations and posters.

  • Tentative oral presentation program
  • Poster session program (posted by 9/12)

There is no cost to attend this symposium due to the generosity of the sponsors listed above but pre-registration is required

Lodging arrangements have not been made for this symposium but a variety of options are available:

The conference will be held in the Alumni Lounge (a.k.a. Nifkin Lounge), Marshall Hall on the SUNY-ESF campus located adjacent to Syracuse University.

Parking has been arranged in the Irving Garage just a short walk from Marshall Hall (campus map).

Tentative Program

Time Place Speaker Title
8:00-9:10 AM Alumni Lounge
Marshall Hall
Check-In
Coffee + Bagels
Poster Setup
Posters on Display
9:15 Alumni Lounge Phil Borer
Syracuse University
Welcome
9:30 Thomas Szyperski
SUNY-Buffalo
Where do we stand on GFT projection NMR spectroscopy?
9:55 Yibing Wu
SUNY-Buffalo
GFT-NMR based high throughput structure determination exemplified for NESG targets NeT4 and SR500A
10:10 Arindam Ghosh
SUNY-Buffalo
NMR structure of NESG target MR32, a member of the family of Trm112p-like proteins
10:25 Bio-Break
10:35 David LeMaster Wadsworth Center - NYS Dept. of Health Electrostatic stabilization and general base catalysis in the active site of the human protein disulfide isomerasea domain monitored by hydrogen exchange
11:00 Joseph Hornack
RIT
The relaxivity of Gd-(DTPA-BMA) / Cu+2 mixtures and evidence for a Gd-(DTPA-BMA)-Cu complex.
11:25 Nelly Aranibar
Bristol-Myers Squibb
Metabolomics in Drug Discovery and development
11:50 Lunch
Poster Session
 
1:30 PM 140 Baker Lab Nikolaos Sgourakis
Rensselaer Polytechnic Institute
Pressure Effects on the Ensemble Dynamics of ubiquitin at the Picosecond-to-Nanosecond timescale investigated with isotropic reorientational eigenmode dynamics
1:55 Paul Giammatteo or John Edwards
Process NMR Associates, LLC
New Developments in Non-traditional NMR Applications
2:25 George Crull
Bristol-Myers Squibb
Extending Solid State NMR to Address Process Development Issues
2:50 Gwen Lubey
P+G Pharmaceuticals
Solid State NMR Characterization of Risedronate Hydrate Forms and Dehydrated Risedronate
3:15 - Break
3:30 Keynote Lecture Prof. Ruth Stark
CUNY
NMR Structural Studies of Protective Plant Biopolymers

October 5, 2007

Process NMR Sessions at Eastern Analytical Symposium - November 14

Filed under: NMR — processn @ 1:26 pm

Eastern Analytical Symposium – November 12-15, 2007
Garden State Convention Center, Somerset, New Jersey

Process NMR Technology Sessions
Wednesday, November 14, 2007
Chair: John Edwards, Process NMR Associates
Sponsored by Process NMR Associates

Process NMR Technology I: High-Resolution Studies

9:00 “Introduction to NMR in Process Control”
John Edwards, Process NMR Associates

9:25 “Standardizing and Stabilizing NMR Calibration Transfer”
Miko DeLevy, Qualion NMR Analyzers

9:50 “More from the Barrel – On-line NMR Increases Diesel Production and Quality”
Paul Giammatteo, Process NMR Associates

10:15 Break

10:35 “Taking NMR into the Refining Process: Best Practices and Benefits”
Marcus Trygstad, Invensys Process Systems

11:00 “Get Your Head Out of the Sand: Use of Reaction NMR to Better Understand Reactions in Process Development”
Andreas Kaerner, Eli Lilly

11:25 “Direct Prediction of Gasoline Properties for Monitoring Refinery Processes by H-1 NMR Spectroscopy”
Veena Bansal, Indian Oil Company

Process NMR Technology II: Time-Domain Studies
Chair: John Edwards, Process NMR Associates
Sponsored by Process NMR Associates

2:00 “Recent Developments in Time-domain NMR and Its Applications in Polymer Industry”
Harry Xie, Bruker Optics

2:25 “Time-domain NMR: Uses and Contributions to Process Control”
Vaughn Davis, Progression

2:50 “Recent Progress of NMR and MRI in Petroleum Exploration”
YiQiao Song, Schlumberger-Doll

3:15 Break

3:35 “Applications of Time-domain NMR to Laboratory and On-line Polymer Analysis”
Maziar Sardashti,ConocoPhillips

4:00 “Challenges in On-line Water Cut Monitoring of Heavy Oil Thermal Operations Using Low Field NMR”
Sergey Kryuchkov, University of Calgary

4:25 “Benchtop Fluoride NMR: A Rapid QC/QA Method”
Chris Borgia, Colgate-Palmolive

 

The Wood-Based Biorefinery in a Petroleum Depleted World

Filed under: NMR, Process NMR, Energy, Chemistry — processn @ 1:08 pm

The Mid-Hudson Section of the American Chemical Society and Vassar College Announce

“The Wood-Based Biorefinery in a Petroleum Depleted World”

Dr. Arthur J. Stipanovic,

Professor and Chair, Department of Chemistry

State University of New York, College of Environmental Science and Forestry (SUNY-ESF)

Wednesday, November 7th, 2007

Time: 7:00 pm

Location: Mudd Chemistry Building, Third Floor

Refreshments will be served at 6:30 pm

Vassar College, Poughkeepsie, New York

Contact: Dr Joseph Tanski (jotanski@vassar.edu, 845-437-7503)

Abstract: The 21st century is envisioned to become the “age of biology” as renewable biomass resources replace petroleum in energy and industrial product applications. Motivated by concerns over national energy security, global CO2 reduction, a need for biodegradable products, and enhanced rural economic development, the engineering and construction of “biorefineries” for the manufacture of fuels, chemicals, polymeric materials and power from renewable resources is now a critical national priority. The context and intent of a biorefinery must be much more than simply replacing crude oil with renewable raw materials. A successful biorefinery must: 1) efficiently separate its raw material source into individual components, and, 2) be able to convert these components into marketplace products. The biorefinery must mirror the efficiency of today’s modern petrochemical refinery in using all components of its raw material source for the production of chemicals, fuels, and power.

Woody “lignocellulosic” biomass is a complex, composite material consisting of three polymers in close association: hemicellulose, cellulose, and lignin plus small amounts of low molecular weight extractives and inorganics. In this presentation, a group of synergistic biomass feedstock and “biorefining” technologies under development at SUNY-ESF, in collaboration with many industrial and academic partners, will be discussed including: short-rotation fast growing willow production, biodelignification, hemicellulose extraction, polymer conversion to fermentable sugars, biodegradable thermoplastics and hemicellulose-based composites.

See the Stipanovic Website at SUNY_ESF for further details…..http://www.esf.edu/chemistry/faculty/stipanov.htm

Bio: Dr. Arthur J. Stipanovic is currently Professor and Chair of the Department of Chemistry at the SUNY College of Environmental Science and Forestry (SUNY-ESF) in Syracuse , NY , and also serves as Director, Analytical and Technical Services. His research interests include biodegradable polymers from renewable resources, high-throughput analytical techniques for determining the composition of woody biomass and new processes for the wood-based biorefinery. Dr. Stipanovic received both his B.S. and Ph.D. degrees from SUNY-ESF in polymer chemistry and much of his career was spent at the Texaco R&D labs in Beacon, NY, in new technology and lubricants research. He is a past Councilor and Executive Board member of the Mid-Hudson ACS section and, more recently, has served as Chair of the Syracuse section.

Directions: Vassar College is located off Raymond Avenue in Poughkeepsie , NY. Refer to the following link for driving directions and campus map: http://www.vassar.edu/directions/. Enter the Main Entrance of the campus on Raymond Avenue and go right towards the Mudd Chemistry Building. The Security Guard at the Main Entrance will direct you to parking.

 

June 12, 2007

NMR Analysis of Jasmine Absolute - jasmine officinale - Egypt

NMR analysis of Jasmine Absolute.

For more information on NMR of Essential Oils visit the PNA website.

May 15, 2007

Omega-3 Dietary Supplements - NMR Analysis

Fish Oils - Flaxseed Oils

NMR is extensively utilized to analyze fish oils and edible oils high in omega-3 fatty acids.

Examples of 1H and 13C data and analysis are provided below:

13C NMR Analysis of Fish Oil Supplement

13C NMR of Flaxseed Oil Supplement

May 14, 2007

Wine Analysis by NMR

Brief Overview of Wine Analysis by 1H and 13C NMR

Wine analysis by 1H or 13C NMR can be used to follow acid content during maturation. Lactic, succininc and acetic acid can be followed readily by both techniques and presence of sugar, glycerol, and methanol can be observed.

Chemometric approaches are starting bear fruit with respect to quantitative analysis:

 

NMR Without Solvents - Biodiesel Production Process - FAME, Glycerol, FFA, and Methanol

1H and 13C NMR NMR is typically obtained using deuterated NMR solvents to lock the field during acquisition. In some cases the use of these solvents is problematic as it prevents observation of solublized phases present in the sample. As an example we show here the NMR data obtained on a biodiesel production process. One of the major issues with the FAME product is the presence of glycerol in the product. NMR analysis is usually performed by dissolving the FAME in CDCl3 in which glycerol is completely insoluble. Thus NMR analysis performed in this way does not allow analysis of residual glycerol content. However, if the FAME is run neat this issue does not arise.
Another analysis of enormous interest from the process control standpoint is the analysis of the glycerol/methanol phase. This phase contains considerable free fatty acids as well as the glycerol by product and excess methanol from the transesterification process. The three components are readily observed by 1H and 13C NMR, and 23Na can be used to observe NaOH content in the phase. Finally the shift and shape of the observed OH resonance can yield information on the pH of the glycerol phase. Typically this analysis is done in DMSO-d6

Below are some examples of NMR obtained without a deuterated solvent:

Difference in aliphatic carbon distribution between FAME phase and Free Fatty Acids (FFA)

found in the glycerol - methanol phase.

1H NMR of aliphatic component found in the FAME phase as well as the FFA in the glycerol phase.

May 10, 2007

NMR PhD Position with Damien Jeannerat at Universite de Geneve

I am posting this on behalf of Damien Jeannerat.

PhD Position Available Starting in September 2007

April 16, 2007

Monitoring of a Biodiesel Transesterification Process with a TD-NMR Spectrometer

 

The 19.5 MHz Spintrack NMR analyzer was utilized to study a FAME biodiesel production reaction. The samples analyzed were: 

1) Used vegetable oil

2) Partially transesterified biodiesel product (bad biodiesel) 

3) High yield FAME biodiesel product 

4) Glycerin by-product from the process

 

CPMG T2 decays were generated and then that data was processed with a inverse laplace transformation to produce T2 distribution profiles.

NMR Experiment explanation is given below:

 

 

The CPMG data obtained on the four samples is shown below:

The T2 distribution profiles obtained by inverse Laplace transformation of the CPMG data are shown below:

 

 

Plainly TD-NMR can play a role in monitoring the biodiesel production process.

 

TD-NMR Analysis of Catalytic Cracker Feedstocks

 

The 19.5 MHz Spintrack NMR analyzer was utilized to study a large series of  vacuum gas oils and FCC feeds for which PNA also has laboratory test data.

 

The analysis was performed on a SpinTrack 19.5 MHz TD-NMR spectrometer - CPMG T2 decays were generated and then that data was processed with a inverse laplace transformation to produce T2 distribution profiles. These T2 distribution profiles are currently being correlated to physical and chemical property data.

NMR Experiment explanation is given below:

 

 

The CPMG data obtained on the four samples is shown below:

 

The T2 distribution profiles obtained by inverse Laplace transformation of the CPMG data are shown below:

 

The correlation between T2 distribution and the metal content, viscosity, distillation range, density, asphaltene content are all being investigated at the current time.

April 15, 2007

13C NMR of FAME Biodiesel

pdf version

Below are examples of 13C NMR data obtained on biodiesel (FAME) and the vegetable oil precursor that it was made from by transesterification process involving microwave activation of the reaction between triglycerides and methanol in the presence of a caustic catalyst. Process NMR Associates is developing correlations between 13C NMR data and biodiesel properties stipulated in ASTM 6751.

Detailed 13C NMR Analysis of Hydrocarbons - Patent Applications

Today one often finds hydrocarbon mixtures described by the detailed carbon type analysis that is possible from 13C NMR.

Many petroleum related products are being described in this way in patents leading to a novel way of describing a material and restricting others from using those same materials in products of their own. See Exxon, Mobil, and Chevron patents such as:

 6,090,989 ;  6,210,559  ;  6,059,955  ;  6,846,778  ;  20050077208  ; and 20050077209

In this PDF file we have shown some of the details present in a 13C NMR spectrum on petroleum products such a base oils, gas oils, diesels, etc.

Details of NMR Analysis

There are some issues with the assignements of many of these patents … for more details on how NMR might be of use in the patent process contact John Edwards

April 14, 2007

NMR Analysis of Hydrocarbonic Solvents

pdf version


Naphtha Chemistry Analysis by 1H NMR

PDF Version

1H NMR has been used extensively by Process NMR Associates to determine PIONA analysis of Naphthas and to determine detailed aromatics breakdown in aromatics unit feeds, products, and intermediate products. Below are a few examples of naphtha chemistries that are observed and quantified by 1H NMR.

Conjugated Olefin analysis is performed by a combination of HH-COSY and 1D 1H NMR.

For more details contact John Edwards

 

NMR Job Opportunity - Saudi Aramco

Saudi Aramco Research and Development are searching for an experienced NMR spectroscopist - see details

Anyone who has NMR employment opportunities should contact Process NMR Associates. We would be happy to post you job listing to our blog and website.

If interested please e-mail a job description, requirements, and contact information to John Edwards

April 13, 2007

Aloe Vera Analysis by NMR

 PDF Version


Adulteration of Acacia senegal (Gum Arabic) Investigated by NMR Spectroscopy

 PDF Version

 

Quantifying Adulteration of Licorice With Maltodextrin by Liquid and Solid-State NMR

Three samples were analyzed to determine if liquid or solid-state NMR techniques could be utilized to quantify adulteration of licorice powders by maltodextrin. Samples analyzed were:

Maltodextrin, Licorice #1, Licorice #2

Licorice #1 and Licorice #2 were analyzed by a combination of liquid-state 1H and 13C NMR on a Varian Unity-300 spectrometer, and solid-state 13C NMR on a Varian UnityPlus 200 spectrometer. The resulting spectra are shown in the attached plots.

One of the Licorice samples is adulterated by maltodextrin to an unknown concentration, the other licorice sample is pure licorice. Which sample was which was not known during the analysis. Initially it was hoped that the addition of maltodextrin to the licorice would be readily observed as new peaks appearing in the spectrum of the licorice sample. However, it can be seen that in both the 1H and 13C NMR there is considerable overlap of the peaks in the spectra of pure licorice and maltodextrin.

When no observable maltodextrin peaks could be assigned it was decided to simply use the quantitative integral data from the regions of the spectrum where the maltodextrin overlaps with the licorice spectrum compared to the integrals obtained from regions solely assignable to licorice. In Tables 1-3 are the quantitative results for each of the experiments performed.

Table 1: 1H NMR Integral Regions

 

Normalized on Reg 4

 

 

 

 

 

 

 

 

Regions 1 and 2 contain maltodextrin/licorice peaks.

Regions 3 and 4 contain only licorice peaks …. Data was norma lized to region 4. The norma lization norma lizes the licorice signal intensity. Thus the increased intensity of regions 1 and 2 in sample #1 is indicative that this sample contains maltodextrin. Samples #1+ and #2+ were made by adding more maltodextrin to the samples. Sample #1+ contains a further 10.9 wt % maltodextrin, while sample #2+ contains 11.4 wt% maltodextrin. The values were used to calculate the maltodextrin content in sample #1.

The 1H analysis indicates that there is 3.3 wt% maltodextrin in sample #1

Table 2: 13C NMR Integral Regions

 

Normalize on Region 7

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Regions 1-3 were common to licorice and maltodextrin signals, while regions 4-7 were exclusive to licorice signals. Normalization on region 7 sets the licorice at a norma lized intensity. Again the intensty of regions 1-3 increases from sample #2 to sample #1 indicating the presence of maltodextrin in sample #1.

Calculation indicates that there  is 6.1 wt% maltodextrin in the sample.

Table 3: Solid-State 13C Integral Regions

 

Solids 13C CPMAS

 

Normalized to Reg 3

 

 

 

 

Region 1 contains maltodextrin and licorice signals, while regions 2 and 3 contain only licorice signals.

Again, the intensity of region 1 increases from sample #2 to 31 upon norma lization of the licorice only region 3. This confirms the presence of maltodextrin in sample #1. Samples #2+ and #1+ were not analyzed by solid-state NMR. This 13C analysis is much faster than the liquid-state NMR and would be a plausible short cut to quantify maltodextrin content.

  Upon completion of the analysis it was revealed that the adulteration value was 5% maltodextrin.

 

PDF Version - AppNote - Spectra

March 30, 2007

Process NMR Symposia to be held at EAS 2007

John Edwards of Process NMR Associates has organized and sponsored two symposium sessions at the Eastern Analytical Symposium in Somerset New Jersey, November 12-15, 2007. One session will focus on high-resolution process NMR and the other on applications of TD-NMR in process control. The speakers and talk titles are listed below. Check the EAS site for exact details on the date and time of the sessions (EAS website). If you are interested in attending and would like to submit a paper for presentation visit the EAS Abstract submission site.

Session Title: Process NMR Technology - High Resolution NMR

John Edwards, Process NMR Associates, “Introduction to NMR in Process Control”

Miko DeLevy, Qualion NMR Analyzers, “Standardizing and Stabilizing NMR Calibration Transfer”

Paul Giammatteo, NMR Process Systems, “More from the Barrel - On-line NMR Increases Diesel Production and Quality”

Marcus Trygstad, Invensys Process Systems, “Taking NMR into the Refining Process:  Best Practices and Benefits”

Andreas Kaerner , Eli Lilly, “Get Your Head Out of the Sand: Use of Reaction-NMR to Better Understand Reactions in Process Development”

Veena Bansal, Indian Oil Corporation, “Direct Prediction of Gasoline Properties for Monitoring Refinery Processes by 1H NMR Spectroscopy”

Session Title: Process NMR Technology - TD-NMR

Harry Xie, Bruker Optics, “Recent Developments in Time-domain NMR and its Applications in Polymer Industry”

Vaughn Davis, Progression Inc, “Time Domain NMR: Uses and Contributions to Process Control”

YiQiao Song, Schlumberger-Doll, “Recent Progress of NMR and MRI in Petroleum Exploration”

Maziar Sardashti, ConocoPhillips, “Applications of TD NMR to Laboratory and On-line Polymer Analysis”

Sergey Kryuchkov, University of Calgary, “Challenges in Online Water Cut Monitoring of Heavy Oil Thermal Operations Using Low Field NMR”

Chris Borgia, Colgate Palmolive, “Benchtop Fluoride NMR:  A Rapid QC/QA Method”

March 25, 2007

Trans Fat Analysis by NMR

 

A series of Trans Fat standards was purchased from AOCS. The ability of 1H and 13C NMR to predict Trans Fat Content as well as 

Saturated, Poly-unsaturated, and Mono-unsaturated Fat Content

The data of the samples is presented in the table below:

 

 

PLS regression techniques were used to correlate 1H and 13C NMR spectral variation to the unsaturation level and type of unsaturation of the samples.

 

Processed 13C data is shown below:

 

 

1H NMR data is shown below:

 

 

The following correlations were obtained from the 13C NMR data.

 

 

 

 

 

 

 

 

NMR Analysis of Essential Oils - Example of Sri Lankan Citronella

The data below shows the ability of 13C NMR to assign the natural product distribution found in essential oils. Once assignment of the oil hgas been obtained by 13C NMR the 1H NMR can also be assigned. For QA/QC a benchtop 60 MHz system has enough resolution that authenticity of essential oils can be performed either visually of by PCA type analysis.

Ger - Geraniol         GerAc - Geranyl Acetate        iEugMe - Methylisoeugenol       Bor - Borneol

aPin - alpha-pinene        Lim -  Limonene        tOci - trans-beta-Ocimene      Cen - Camphene

Cllo - Citronellol        Clla - Citronellal        GenD - Germacrene D         aCal - Citral A (Geranial)

aTol - alpha-Terpiniol         cOci - cis-beta-Ocimene        Myr - Myrcene

March 24, 2007

Process NMR for Transesterification Monitoring and Certification of Biodiesel

1H NMR has been used extensively to analyze biodiesel the vegetable oil feeds, reaction intermediates, and final products of the biodiesel transesterification process.

See Oliviera et al, Talanta 69 (2006) 1278-1284 and Gnothe, J. Am. Oil Chem. Soc 78, 1025-1028 (2001)

The final biodiesel product is a B5 (5% Biodiesel) or B20 (20% Biodiesel) blend of biodiesel in refinery produced diesel fuel. Researchers have performed method developments to analyze the biodiesel content in diesel fuels by NIR using 1H NMR as the primary method to quantify the biodiesel content. (See Jin et al, Fuel 86(7-8), 1201-1207 (2007) and Knothe J. Am. Oil Chem. Soc. 77 489-493 (2001). Process NMR at 60 MHz can be used to quantify the biodiesel directly. Below is an example slide of a biodiesel 1H NMR spectrum compared to two different diesel fuel spectra.

 

The chemistry that is directly observed in the NMR spectrum as well as the distinct chemical regions that are present in the diesel and biodiesel make this analysis relatively straightforward. Chemometrics can be used or quantitation can be obtained directly from a simple spectral calibration.

Biodiesel Production Monitoring

NMR can be used to follow the reaction of biodiesel directly, the following slides show the steps in the transesterification process.

 

 

Glycerol content in the biodiesel or unconverted vegetable oil content can be determined easily directly from the spectrum.

Expansion of Incomplete Reaction Series

 

Work is currently underway to develop NMR calibration models that can predict the various quality parameters specified in ASTM D6751 for biodiesel.

These calibrations, based on either 1H or 13C NMR, when validated would allow rapid testing of biodiesel production batches and would make complete analysis of small production batches economically feasible (there is no point making 300 gallons of biodiesel if you have to perform $1300 of testing on the batch).

 

 

February 7, 2007

Process NMR Technology Session Planned for Eastern Analytical Conference 2007

Press Release - NMR Process Systems - Danbury CT - February 14, 2007  

Dr Edwards of Process NMR Associates has been asked to organize a session on Process NMR Technology at the Eastern Analytical Conference to be held at the Garden State Exhibit Center, November 12-15, 2007. Below is a copy of the Call for Papers sent out on February 14, 2007. 

Hello to all,

I have been asked by Cecil Dybowski to chair a session on Process NMR Technology at the 2007 Eastern Analytical Symposium to be held November 12-15 at the New Jersey Garden State Exhibit Center in Somerset New Jersey. At this point I am putting out some feelers to gauge the level of interest that is out there amongst NMR practitioners in this field. I would like the session(s) to encompass both high resolution and time-domain applications of NMR in process control applications and at-line in manufacturing facilities in all industry sectors. The work can be actual on-line examples or laboratory based analysis being used to justify or prove applications before they are spun out to the plant. Developments in hardware, software and chemometrics would also be of general interest and to this end hardware talks on magnet and NMR-sensor development and their potential application would be encouraged. Fully automated NMR analysis in the laboratory that simply requires a technician to load the samples would also be considered as a valid topic.

The abstract deadline for EAS is April 15th. If you are interested in presenting a paper I would appreciate hearing from you by e-mail. Once I know how much interest is out there I will begin pulling the details together and have the speakers submit abstracts through the EAS website. For your information the EAS is the premier analytical meeting for the U.S. East coast and it has a website at http://www.eas.org. Also, as an introduction to the symposium itself, I am providing a link to the program chairs letter - http://www.eas.org/symposium/symposium.html

The distribution I have included in this e-mail are of persons and organizations that I know are working in this field. If you have any colleagues, customers, or acquaintances who you feel could provide a good presentation on their research or applications please feel free to forward this e-mail on to them, or inform me of their e-mail address and I will contact them.

I look forward to hearing from you and hope that you will join us in New Jersey,

Best Regards,

John

Contact : John Edwards, (203) 744-5905  E-Mail: john@process-nmr.com

January 22, 2007

Process NMR Spectroscopy Seminar Series to be Held at 2007 Eastern Analytical Symposium

John Edwards of Process NMR Associates has agreed to chair a session at the Eastern Analytical Symposium in Somerset, New Jersey in November, 2007. The session is entitled “Process NMR Spectroscopy”. If you are interested in presenting a technical paper at this session please contact John directly at john@process-nmr.com

Also listed here is the 2007 Call for Papers for the upcoming meeting.

Dr John Edwards Joins ACS Speaker Service

Dr Edwards of Process NMR Associates recently joined the American Chemical Society (ACS) speaker service which provides a clearing house for speakers who lecture on chemistry topics at local ACS Section Meetings that are typically held once a month during the academic year. Dr Edwards’ talk abstract and bio are provided below. Feel free to contact Dr Edwards if you are interested in hosting his talk at your meeting.

Biographical Sketch

Dr. John C. Edwards

Dr Edwards is currently a partner in Process NMR Associates, LLC where he is responsible for commercial analytical NMR services as well as development of on-line and at-line applications of NMR technology. He received his B.Sc. in Chemistry from Durham University in the UK (1986), and then received his Ph.D. in Physical Chemistry from the University of South Carolina in 1990. His doctoral studies involved solid-state NMR of catalyst materials. He was responsible for all NMR services with Texaco Inc from 1990-97 where he developed his particular expertise in petroleum and petrochemical NMR. In 1997 began Process NMR Associates which is involved in application of high resolution NMR spectroscopy for on-line process control as well as providing commercial analytical NMR service to over 250 industrial and academic customers around the world. Over the past 20 years Dr Edwards has developed an expertise in many types of non-traditional NMR equipment and applications.

Abstract

The Wonderful World of Non-Traditional NMR Spectroscopy

Over the past 60 years NMR has developed into a premier spectroscopic tool in the academic and industrial world. Superconducting spectrometers with fields ranging from 7 to 23 Tesla are considered as typical NMR equipment and NMR “cold probes”, operating at near liquid Helium temperatures, are now hot items to improve sensitivity and throughput. NMR technology has also found other application areas to exploit and these areas are a far cry from a laboratory environment. Permanent magnet based NMR systems are currently used to map the underground hydrocarbon-water makeup of oil drilling wells and to control huge production units in refineries and chemical plants based on observed proton chemistry. Portable NMR systems are taken into the field for on the spot analysis of agricultural products, antarctic ice, elastomer performance, concrete and wood moisture analysis. Single-sided NMR probe/magnet sensors are being used to study degradation of antique books, frescoes, and paintings. The non-traditional NMR technology and applications will be described and the economic benefits of the applications will be discussed. The future of NMR will include small, affordable, automated systems that will make NMR a much less exotic technique reserved only for large budget industrial or academic facilities.

Contact : John Edwards, (203) 744-5905 E-Mail: john@process-nmr.com

January 19, 2007

Flying J Selects On-Line NMR Technology from NMR Process Systems LLC for Clean Fuels Production and Expansion Program at Bakersfield Refinery

Press Release - NMR Process Systems - Danbury CT - January 19, 2007

As part of its announced multi-million dollar refinery improvement prog ram , Big West of California, LLC has selected NMR Process Systems LLC (NPS) to provide on-line NMR technology. The NPS integrated sampling and NMR analyzer system will enable the refinery to both increase its diesel production, as well as achieve quality targets needed for the new Clean Fuels Flying J will produce at it’s Bakersfield, CA, refinery. NPS’s NMR technology solutions, coupled with a Swagelok® sampling system, will perform simultaneous, multi-property diesel measurements required for process monitoring and control in the manufacturing of these new fuels. Installation is scheduled for the first quarter of 2007.

NMR Process Systems LLC, of Danbury, Connecticut (www.nmr-automation.com) is a process analytical technology and engineering services company, providing process analytical solutions to maximize plant and manufacturing operations in the refining, petrochemical, pharmaceutical and food industries. Solon, Ohio based Swagelok Company (www.swagelok.com) designs, manufactures, and delivers an expanding range of high-quality fluid system products and solutions.

Contact:
Paul J. Giammatteo
Product and Marketing Manager
NMR Process Systems, LLC
87A Sand Pit Road
Danbury, Connecticut 06810
Tel: +1-203-744-5905
paul@nmr-automation.com
www.nmr-automation.com

December 28, 2006

Old Swan - NMR Software Blog

Since October 2006 “Old Swan” has been posting an excellent blog on NMR software. It can be found at nmr-software.blogspot.com

It makes very interesting reading … though I’m not always sure what is going on - see the December 11th posting

New Site Dedicated to Magnetic Resonance in the Food Sciences

A new website has been introduced that focusses on the applications of Magnetic Resonance (NMR, MRI, Relaxometry) to the chemistry and physics of foods. The website can be found at magres.foodsciences.org

This organization also arranges the biannual conference on Application of Magnetic Resonance in Food Science - they have an excellent poster session with PDF versions of the poster presentations published to the web - Poster PDFs

December 6, 2006

Dairy NMR Database of Lignin and Cell Wall Model Compounds.

This excellent database can be downloaded from http://ars.usda.gov/Services/docs.htm?docid=10491

This is what the authors (Sally A. Ralph, John Ralph and Larry L. Landucci.) said about the database:

“This NMR database has been designed to aid plant cell wall chemists in general and lignin chemists in particular. By compiling data from a series of model compounds run under strict acquisition conditions in three solvents, we hope to provide a compilation useful for cell wall NMR research.”

September 28, 2006

International Humic Substances Society

International Humic Substances Society – details on standard humic and fulvic acid isolation methods – standard materials – NMR reference data on standard materials.

 

NMR Meetings and Society Links

Filed under: Analytical NMR — Administrator @ 9:36 am

A few society websites to keep an eye out for meetings as well as a few meeting links that I have come across recently.

International Society for Magnetic Resonance in Medicine

Clinical Magnetic Resonance Society

European Society for Magnetic Resonance in Medicine and Biology

Japanese Society for Magnetic Resonance in Medicine

Society for Cardiovascular Magnetic Resonance

Magnetic Resonance Managers Society

RSC NMR Discussion Group

Finnish NMR Discussion Group

Spanish Magnetic Resonance Society

Austrian NMR Discussion Group

Australian and New Zealand Society for Magnetic Resonance

German Magnetic Resonance Discussion Group

Italian Magnetic Resonance Discussion Group 

49th Rocky Mountain Conference on Analytical Chemistry – July 22-26, 2007 – Beaver Run Resort, Breckenridge, Colorado 

Endorsed by the Colorado Section – American Chemical Society and the Rocky Mountain Section – Society for Applied Spectroscopy
Related Links:
 

5th Alpine Conference on Solid-State NMR

11th Brazilian NMR User Meeting / Workshop: NMR in South America – May 7-11, Rio de Janeiro State, Brazil

For information please contact Sonia Cabral de Menezes

45th Annual Meeting of The NMR Society of Japan  Nov. 22-24, Kyoto, Japan   
 
MRS Symposium “Magnetic Resonance in Material Science”  Nov. 27 – Dec. 1, Boston, Massachusetts, USA
 
For further NMR meeting info visit  http://www.process-nmr.com/meetings_and_events%202006.htm

 

September 27, 2006

Interactive NMR Frequency Map With IUPAC NMR Data

A very useful NMR frequency/receptivity map from Alexej Jerschow at New York University – Interactive Map and Table

 

Excellent Article on “Mobilizing Magnetic Resonance” from Physics World

An excellent view on the latest new technologies appearing on the scene of mobile magnetic resonance. Though the review is fairly thorough in the “new technologies”, it does not mention the mobile permanent magnet based spectrometers currently availbale from Process NMR Associates. I don’t know why traditional mobile NMR instrumentation is repeatedly ignored in this arena. The perception is out there that NMR will always be expensive to buy, maintain and operate. The truth of the matter is that high-resolution NMR instrumentation should cost less than $100K and low field relaxometers should cost below $30K. Automation is possible for all aspects of NMR operation from locking, shimming, pulse sequence calibration, gain settings, and post processing procedures. I’d love to hear comment from people on this as I’ve been scratching my head for years as to why people aren’t interested in low field spectrometers anymore for undergraduate and industrial applications.

September 25, 2006

NMR of Earwax

Yet another masterpiece from tenderbutton – NMR of earwax.

September 19, 2006

EUROMAR 2007 - Magnetic Resonance Conference

The EUROMAR 2007 magnetic resonance conference will be held in Tarragona, Spain, July 1-6 at the Tarragona Trade-Fair and Congress Centre. Satellite meetings will be held on July 6.

September 15, 2006

SMASH Conference 2006: Multi-Sample MAS Probe

I was at the SMASH conference in Burlington Vermont earlier this week and the presentation of the week in my opinion was the multi-sample MAS probe poster by Nelson et al. This is a probe based on a patent (6,937,020) filed by Professor Eric Munson’s NMR group at the University of Kansas, and built by David Lewis of Revolution NMR. The concept involves stacking multiple MAS rotor housings in the probe head and then shuttling them into the central sweet spot of the magnet for acquisition via a pneumatic device attached at the base of the probe. The RF is switched between independent RF inputs and each housing has an independent tune/match capability. The idea is to increase throughput by allowing extra acquisitions to be obtained on other samples during the relaxation delays of the independent experiments.An excellent video demonstration is available on the webpage dedicated to the probe, as well as references to the patent and the journal article covering the development (“Multiple-sample probe for solid-state NMR studies of pharmaceuticals”, Solid State Nuclear Magnetic Resonance 29 (2006), 204 – 213). Commercial release is expected in 2007.

July 28, 2006

New CAPP NMR Method - Olefin Content of Crude Oils, Condensates, and Diluents by 1H NMR

The Canadian Association of Petroleum Producers has produced a test method to quantify olefins in crude oils, condenates and diluents. The method is particularly aimed at heavy oils and bitumens and their products that are not amenable to traditional olefin analysis. The method is published at the following link. We have developed many methods similar to this and have the ability to quantify and speciate the olefins present in the sample. The current CAPP method developed by the Canadian Crude Quality Technical Association (CCQTP) can be used to obtain total olefin content. Further NMR analysis and a few other experiments would allow some more detailed olefin chemistry distributions to be determined as well as observe the presence of conjugated diolefins that would be particularly troublesome in the processing of these materials. 1H NMR spectroscopy can be used very effectively to obtain many chemical and physical properties of crudes, heavy crudes, bitumen, and the distillate products that are produced by these materials. 1H NMR spectral correlation with these properties by PLS or non-linear PLS regression can yield extremely robust models, and for the chemical properties much more detailed chemical structure information can be obtained fro combining 13C NMR data with 1H NMR results.

CCQTP is an association with members that span multiple segments of the Canadian oil industry -it’s history, mission, and membership can be found at the site.

On a related note an excellent technical site dealing with crude oil quality issues cane be found at the Crude Oil Quality Group website, which is a consortium with the following membership, dedicated to developing test methods and quality standards for crude oil trading that go well beyond the traditional gravity and sulfur measurements currently used. There are many additives, processing fluids, corrosive materials that can be found in crude oils that can cause processing issues for the buyer who purchases simply based on density and sulfur. The group has made public much of it’s meeting agenda archives and the presentations given at those meetings. It is an interesting read for those interested in petroleum chemistry issues.

At PNA we have been developing some high field and low field NMR techniques, looking at chemistry and relaxation in crude oils with naphthenic acid and corrosion issues. We would be interested in hearing from anyone interested in woprking with us to develop a relatively straight forward method for NAN and TAN analysis by NMR methods. 

Quantitative NMR

Found and interesting site touting quantitative NMR as a new concept….seems strange as 99% of the NMR work I have done is considered quantitative. There is a perception out there that 13C NMR is always qualitative. This has been confirmed to me in conversations with organic chemistry professors who will perform quantitative 1H NMR all day long and even justify higher magnetic field instruments based on lack of resolution in 1H data as they have the perception that 13C is purely qualitative and don’t think of the superior resolution and chemical shift information present in 13C spectra. The website is at qnmr.com, and contains an excellent petroleum chemistry example of the development of quantitative 13C NMR for aromaticity determination by Joe Ray, ex Amoco NMR researcher.

There is also an excellent link to a paper on the quantitative NMR of natural products.

Excellent Solid-State NMR Overview at Durham University

There is an excellent overview of solid-state NMR at my alma mater Durham Univeristy in the UK. The page can be found at the following link.

July 21, 2006

What a day! Took my NMR home with me at the end of the day !

Yesterday started typically, ran a few 1H NMR for some customers, developed a low-field NMR method for diesel and kerosene hydrogen content correlated to aromaticity, try to run some fibers for moisture and spin-finish. Suddenly 5:30 loomed, the Mrs called to ask when I’d home for dinner ….. so rather than incur the wrath of the spouse by continuing late with the work, I simply picked up my NMR and went home with it. The new SpinTrack 20 MHz system is essentially a desktop computer sized console with a 6×6x6 inch magnet weighing 14 lbs. The whole shabang runs off a USB connection to my laptop. Thus …. I spent today completing the work from the comfort of my home office … Beautiful ! Tomorrow I might just carry the system upstairs, put it on the coffe table and acquire some more data while watching the Tour de France on TV. Not many people can say they take their NMR machines home with them at night. This could become a regular thing for me.

July 19, 2006

Interesting News on High Temperature Superconductor Systems

Surfing the web I came across a surprising announcement … it appears that Progression Systems is interested in developing a 80 MHz high temperature superconductor electromagent system to utilize in their process NMR business. Does this mean that Progression will be entering the high resolution NMR domain or raising the resonance frequency and sensitivity of nuclei other than proton (27Al, 23Na, 31P, etc.)? Below is the news bulletin from Industrial Research Ltd (News Bulletin found at: http://www.irl.cri.nz/newsandevents/Mediareleases/joint-venture-for-hts110.aspx).

Joint venture for HTS-110

A new joint venture between HTS-110 and US company Progression Inc will provide customers with a unique high temperature superconducting (HTS) magnet capability.

1 May 2006

HTS-110 Limited, an affiliated company of Industrial Research, focuses on HTS solutions for medical, scientific, energy, defence, transport and industrial markets. Progression is a world leader in the development and implementation of process Nuclear Magnetic Resonance (NMR) technologies, Laser Induced Breakdown Spectroscopy (LIBS) techniques, and Laser Induced Fluorescence (LIF) analysers for the mining, petrochemical, and polymer/polyolefin industries.

The new venture, Progression-HTS-110, will provide customers with unique high temperature superconducting (HTS) magnet capability. The new series of analyser will operate at 80MHz with the field strength of 2 Tesla generated by a HTS magnet.

Target markets for the analyser will include refining applications in the oil and gas industry, educational research and development, pharmaceutical and biochemistry applications.

Chief executive of Progression, Vaughn E. Davis, says the company is looking forward to working with HTS-110 Ltd and describes the deal as the perfect complementary vehicle to extend and build on the unique strengths of Progression’s leading market position in process NMR.

Chief executive of HTS-110, Dr Sohail Choudhry, says it is a strategic move to partner with Progression and extend HTS-110’s leading-edge technology into new markets.

“HTS is an advanced and rapidly developing new technology and we look forward to using that as a key driver for expanding the marketplace with Progression.

“Progression is an innovative company and we share a similar culture – that will work to our advantage and allow us to benefit from both our unique and complementary skills.”

It is anticipated the new company will be headquartered in Houston, Texas, under the leadership of Mr. Scott Simmons.

HTS-110 is a subsidiary company of Industrial Research Ltd – it’s HTS magnet technologies are described here.

July 17, 2006

Abstracts Available for Magnetic Resonance in Food Science Meeting

The Abstracts for the Posters and Speaker Sessions of the 8th International Conference on The Application of Magnetic Resonance in Food Science (July 16-19, 2006) can be found at the following locations – Poster Abstracts and Speaker Abstracts .

July 13, 2006

Stelar Develops New Benchtop FFC Spectrometer and Forms JV Company Invento

Stelar s.r.l. has announced that it will be producing a new benchtop design for it’s Fast Field Cycling NMR product becoming available in September 2006, and also the availability of a new single board NMR console - available June 2006. the company has also formed a JV company called Invento s.r.l. which is a combination of Stelar and a business incubator at the Univerity of Torino. The mission of Invento is to further the development of FFC NMR techniques as standard methodolgies in testing laboratories and to perhaps replace other TD-NMR spectrometers.

July 11, 2006

NMR Monitoring of Magnetic Field Strength of CERN Large Hadron Collider

A group of physicists at the University of Manchester are developing NMR probe technologies to monitor the magnetic field strength inside the solenoids of the Atlas LHC at CERN. The probe technology and accompanying NMR spectrometers are described on the Manchester website.

July 3, 2006

Process NMR Paper at San Francisco ACS Meeting - September 2006

ENITechnologie will be presenting a paper on the on-line application of NMR in lube plant operation at the upcoming ACS Meeting in San Francisco

Experiencing Process MRA Industrial Lube Plant Application – Roberto Giardino1, Silvia Guanziroli1, Cinzia Passerini1, and Antonio Farina2. (1) EniTecnologie S.p.A, via Maritano, 26, San Donato M.se (MI), 20097, Italy, (2) Divisione Refining & Marketing – Raffineria di Livorno, Eni S.p.A, via Aurelia, 7, 57017 Stagno (LI), Italy

In a conventional base oil production plant the operating conditions needed to produce products at a desired specification are very sensitive to feed quality. At Livorno refinery an on-line Process Magnetic Resonance Analyzer (MRA) has been installed to identify the feedstock and product composition and properly set an advanced process control system. By using MRA it is possible to reduce the product quality give-away due to feed quality variation. In this work the industrial experience acquired is reported.

Characterization, On-Line Monitoring, and Sensing of Petroleums and Petrochemicals 8:30 AM-11:30 AM, Thursday, 14 September 2006 Sheraton Palace—Telegraph Hill

Division of Petroleum ChemistryThe 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006

June 19, 2006

Application Overview for Spin Track TD-NMR Spectrometers

Due to it’s broad versatility the Spin Track NMR Hardware supports all standard NMR routines such as AOCS Cd 16b-93, AOCS Cd 16-81, ISO 8292, IUPAC2.150 and creative scientific research. Spin Track has been successfully approved in the food and polymer industries for routine analysis. If your application is not described below please contact John Edwards for discussion. 

Solid Fat Content (SFC) Analysis
The quality of food products containing fats and oils depends on solid fat content (SFC). SFC determination is an essential measurement in the baking, confectionery, and fat industries. NMR has been established as the method for SFC determination by ISO 8292. Measurements of SFC by the Spin Track NMR analyzer can be performed quickly and accurately with great benefit for the manufacturer. 

Simultaneous Rapid-Determination of Oil and Water in Seeds
Sunflower, soybean, groundnut, rape and mustard are appreciated for their oil content, but excess of water content reduces their price. Thus, an accurate and fast determination of oil and water content is important to both manufacturers and customers. The Spin Track NMR analyzer meets ISO 10565 requirements and gives the possibility to simultaneously determine of oil and water content.

Oil/Fat and Moisture analysis in Chocolate, Powdered Milk, Cheese and other Food Products
Time of storage of food products depends strongly on moisture content. Excess moisture leads to microbiological activity and can make food consumption dangerous. Fat and moisture content also heavily  influence taste. Manufacturers are also regulated to disclose the exact information on the fat content of their products. NMR is the most rapid and exact method to determine these essential parameters. The Spin Track NMR analyzer is especially suitable for regular analysis of food quality. 

Curing Degree and Elasticity Analysis in Rubber-Type Materials

Over the past years Rheology has become widely accepted as a tool in the investigation of rubber properties. However, rheological testing equipment can  be extremely expensive and complicated. NMR is very sensitive to the structure and properties of investigated rubber materials. The Spin Track NMR-analyzer allows investigators to obtain data complementary to rheology and can also prove to be more informative. 

Moisture and Crystallinity Analysis in Polysaccharides
Polysaccharides like chitin, chitosan etc. are widely used because of inherent unique properties. Adsorbents and food bio-additions based on them require a regular check of quality. Spin Track NMR-analyzer allows investigators to obtain information about moisture, crystallinity, purity and structure of polysaccharides.

Porosity of Rock Cores/Heterogeneous Catalysts/Zeolites
The possibility of oil development can be defined more exactly in the initial stages of exploration by using NMR. Rock cores saturated by bitumen or water provide information on degree of saturation, structure of saturating compounds, porosity, and diffusion characteristics. This information allows the prediction of oil production yields. The Spin Track NMR-analyzer with a 35mm probe gives the possibility to obtain such information.

Scientific applications
The spectrometer’s Relax software allows construction of many types of NMR pulse sequences, user-defined interfaces, data processing (digital experiments filtering, fitting, Fourier and Laplace transforms) and data manipulations. Thus, customers can directly run automated standard type NMR experiments just by “pressing one button” in the program shell, or create new applications using the powerful pascal-like script language. Widely used experiments like measurements of T1 and T2 (90-tau-90, 180-tau-90, CPMG, FID, Spin Echo, Solid-Echo) are included into the Relax software as default examples. The NMR measurements can be accompanied with the high precision calibration samples and built-in software calibration procedures. Easy automatic tuning of the NMR frequency, pulse-durations, TX power and RX gain is included into the software package. 

Process NMR Associates Begins Marketing of Cutting Edge TD-NMR Spectrometer

Resonance Systems Ltd. has granted Process NMR Associates the rights to promote, market, and sell it’s NMR products and custom NMR hardware in the Americas, and Worldwide. The basic product of the company is a portable NMR-analyzer called Spin Track that can be used for many different low and high resolution NMR applications.

Spin Track meets the requirements of many relaxation and diffusion based NMR analyses:

Food industry (Solid Fat Content Analysis, Dairy Products, Oil and Moisture in Chocolate, Powdered Milk, Cheese and other food products; Oil and Moisture in seeds, Emulsion Characteristics)
Lipid Analysis – Fatty Acid Distribution
Cellulose and paper manufacturing (Moisture/Crystallinity Analysis, investigations of ageing effects)
Oil industry (rock cores analysis, oil-water, oil-water-gas, viscosity, physical property correlation, )
Polymer and rubber industry (Curing degree and elasticity analysis, polymer ageing, glass transition, amorphous/crystalline content)
Chemical industry (Density, Melting Points, Copolymer Ratios, Compatibility, Cure, Cross Linking, H or F content,
Medicine (NMR Surface Analysis of Patients, Plasma Analysis)
Environmental (Water Pollution, Forest Degradation, Soils, Fertilizers)
Fibers – Moisture and Finish Content
Pharmaceuticals (Tablet Analysis, Coatings/Components/Moisture, Hydrogen/Fluorine/Sodium Content)
Relaxation, Diffusion, Particle Size, Pore Size Distribution

Utilization of mobile NMR measurement equipment from Process NMR Associates provides the following advantages:

Reduction of expenses associated with meeting quality requirements of products
Simplicity of use in routine production measurements and in advanced laboratories for complicated analysis
Mobility of the hardware and low cost for the overall device
Non-invasive measurements of any sample
Hardware solutions for non-standard NMR applications
Permanent technical support and comprehensive scientific consulting
Fair price and absolute ease of operation!

Portable Low-Resolution NMR Analyzer

Spin Track Spectrometer

Analyzer is designed to perform:

All standard NMR applications
Development of new NMR-based techniques
Teaching quantum physics, NMR, analytical chemistry in Universities and Colleges

NMR analyzer Spin Track comprises functional parts (probes, preamplifier and duplexer, TX Power Amplifier, Sequence Generator and PC Interface, Data Acquisition System, NMR Transceiver) which can be purchased separately and used for the specific needs of an advanced customer (see example of connection assembly). Depending on the required magnet system the Spin Track can be used as NMR relaxometer or high resolution NMR spectrometer.

Basic characteristics of Spin Track analyzer:

Frequency range of the NMR spectrometer module: 5..60 MHz
Ringing time for 10 mm NMR probe is 8 ms
Probe tube diameter: up to 35 mm
Changeable preamplifiers and 50 Ohm matched duplexers with self bandwidth of 5 MHz
Customer-defined set of sensors (5, 10 and 30mm test-tube magnet systems, NMR surface sensors)
Adjustable TX output power up to 400 Watts
Adjustable RX channel gain up to 107
RX Sensitivity better than 1 mV (conditions: signal to noise ratio 3)
Adjustable digital filter bandwidth from 100 Hz up to 1 MHz
Pulse sequence length up to 64K events with resolution 100 ns
Quadrature 64Kx10-bit data acquisition system
Complete control of functions via personal computer – USB 2.0 Connectivity
Fast sensors replacement
Compatible with all Microsoft® Windows® operating systems

Software

Relax Software

The product software, Relax, is a powerful tool containing many standard NMR relaxation routines and applications, and can also be used to create new pulse-sequences, pulsed field gradients, gains and attenuations, post-processing methodolgies of considerable complexity. The built-in script language is based on a widespread Pascal syntax and is enriched with commands for fitting, Fourier and Laplace transforms, Low-pass filtering, etc. The script supports dialogue windows, static messages, user-defined diagrams, data manipulation procedures. Relax also allows direct processing of data obtained when utilizing Spin Track as a high-resolution NMR spectrometer.

Stationary Low-Resolution TD-NMR Analyzer

Stationary Spin Track

Analyzer is designed to perform:

Standard routine NMR applications
Development of new NMR-based techniques
Teaching quantum physics, NMR, and analytical chemistry in Universities and Colleges

The Spin Track Stationary fulfills all requirements to conduct NMR measurements like portable version of NMR analyzer.
In addition it is supplied with the possibility for increased probe volume to facilitate excellent statistical averaging of experimental results or to accomodate large samples.

Basic characteristics of Stationary Spin Track Analyzer:

Frequency range of the NMR spectrometer module: 5..60 MHz
Ringing time for 10 mm NMR probe is 8 ms
Probe tube diameter: up to 35 mm
Changeable preamplifiers and 50 Ohm matched duplexers with self bandwidth of 5 MHz
Customer-defined set of sensors (5, 10 and 30mm test-tube magnet systems, NMR surface sensors)
Adjustable TX output power up to 400 Watts
Adjustable RX channel gain up to 107
RX Sensitivity better than 1 mV (conditions: signal to noise ratio 3)
Adjustable digital filter bandwidth from 100 Hz up to 1 MHz
Pulse sequence length up to 64K events with resolution 100 ns
Quadrature 64Kx10-bit data acquisition system
Complete control of functions via personal computer – USB 2.0 Connectivity
Fast sensors replacement
Compatible with all Microsoft® Windows® operating systems
Relax Software

Educational Low-Resolution TD-NMR Spectrometer
Analyzer is designed to demonstrate NMR spin dynamics as well as provide a basic platform for undergraduate level chemistry and physics labs.
Standard routine NMR applications (FID, Spin Echo, CPMG, Carr-Purcell, T1-Determination (90-90 or inversion recovery))
Development of new NMR-based techniques – software allows development of pulse sequences by students without risk of instrument damage.
Teaching quantum physics, NMR, and analytical chemistry in Universities and Colleges

Basic characteristics of Stationary Spin Track Analyzer:
Frequency range of the NMR spectrometer module: 10..20 MHz
NMR Probe tube diameter: 5 mm
10-20 MHz Magnets, Surface NMR Sensors
Changeable preamplifiers and 50 Ohm matched duplexers with self bandwidth of 5 MHz
Adjustable TX output power up to 100 Watts
Adjustable RX channel gain up to 107
RX Sensitivity better than 1 mV (conditions: signal to noise ratio 3)
Adjustable digital filter bandwidth from 100 Hz up to 1 MHz
Pulse sequence length up to 64K events with resolution 100 ns
Quadrature 64Kx10-bit data acquisition system
Complete control of functions via personal computer – USB 2.0 Connectivity
Compatible with all Microsoft® Windows® operating systems
Relax Software

Custom NMR Components
For NMR engineers and advanced specialists Process NMR Associates offers accessories to upgrade, modernize, or build new NMR related devices (see connection example). All modules can be purchased separately and modules can be developed with unique characteristics to fulfill special requirements of the customer.

Surface NMR Sensors         NMR Sequence Generator

Data Acquisition Unit           Wide-Band NMR Transceiver

NMR Power Amplifier           NMR Pre-Amplifiers and Duplexers

For more information and pricing please contact John Edwards

Back to Process NMR Associates Home Page

June 1, 2006

United States Department of the Interior - Oil Shale and Tar Sands Leasing Programmatic EIS

The public forum site of the department of the interior related to the environmental impact statement is found at the following location. The site contains excellent overviews of the tar sands and oil shales found in Wyoming-Colorado-Utah. Excellent Oil Shale site from the DOE with strategic significance reports and government policy statements.

Bruker BioSciences Corporation Announces Agreement to Acquire Bruker Optics Inc.

An interesting news article from Bruker world – “Bruker BioSciences Corporation Announces Agreement to Acquire Bruker Optics Inc. for $135 Million in Cash and Stock” dated April 17, 2006. Fascinating…. of particular interest from the process analytical and molecular spectroscopy side was Bruker Optics VP Dan Klevisha’s comment – ” For Bruker Optics, becoming part of a larger and public company will also allow us to explore complementary acquisitions.”

Materials Research Society - Symposium on Magnetic Resonance in Material Science

Filed under: Process NMR, Analytical NMR, Chemistry — Administrator @ 9:33 pm

The Materials Research Society announces a call for papers for it’s Symposium (MM) on Magentic Resonance in Material Science to be held at the Fall Meeting in Boston on November 27 – December 1, 2006. Abstracts are due by June 20th.

Alternative Sources of NMR Equipment - Beyond the Big 3

There are a number of alternatives to buying new systems from Bruker-Varian-JEOL. A number of third party suppliers are present in the market selling and supporting refurbished used NMR systems. These companies can install and warranty the systems as well as maintain the cryogens for you if you wish. The companies that specialize in supercon NMR systems are Triangle Analytical, RS2D, NMR Associates, and MR Resources. A great place for used probes and repair is J S Research. Consoles can be obtained from Tecmag and from Anasazi (Anasazi also provides refurbished 60 and 90 MHz electro/permanent magnet systems). Spincore provides NMR spectrometer components for those who want to build their own instruments. Magritek, Minispec, Oxford Instruments, Resonance Systems, Progression, PCT, all sell TD-NMR instruments.

Process NMR Associates can guide you through this maze of choices.

May 31, 2006

Stan’s NMR Blog - Two Articles on Magnetic Field Noise Effects

Stan Sykora continues to expand his excellent NMR blog with two new articles on NMR signal reproducibility. His articles cover how field noise effects the repeatability of NMR signals such as FIDs and spectra and Hahn echoes and CPMG trains. In our experience of online NMR we have worked extensively on this topic with respect to the repeatability of the processed NMR spectrum and it’s effect on the repeatability/reproducibility of the chemometric predictions employed for process control. As Stan notes, if people have done a lot of work in this area it is certainly not being reported … mea culpa.

FAPRI World Agricultural Outlook 2006

The Food and Agricultural Policy Research Institute has published it’s annual U.S and World Agricultural Outlook for 2006.

May 30, 2006

Online TD-NMR Analyzers for 19F and 31P Analysis of Minerals and Phosphates

I guess you learn something everyday… The Harrison R. Cooper Systems Company of Bountiful Utah has been marketing low field Phosphorus-31 and Fluorine-19 NMR analyzers for a phospate mineral benefication process and for fluorine monitoring in mineral slurries. It appears from the site that only a few installations were made and no indication of successful outcomes or benefits are provided in the analyzer and process descriptions. I can’t decipher where the NMR technology originated….perhaps Auburn?

May 26, 2006

21.1 Tesla Quench Video

The University of Colorado Health Science Center installed a pumped 900 MHz system in 2005. They have an awesome video of a deliberate quench of the magnet as part of the ramping protocol. Here is the link to the video and here is a link to the NIH funded facility.

1H and 13C Shifts of Common NMR Solvents - Excel Table

Edward Vawter of QD Information Services has made available two useful excel spreadsheets containing the 1H chemical shifts and 13C chemical shifts of most common deuterated NMR solvents. He also has a few other useful articles available from his download page.

Hilarious NMR Adventures at Stanford

Dylan Stiles at Stanford has an often hilarious blog category dedicated to the NMR aspects of his natural product synthesis projects. He gets a lot of commentary which is great as I think he has the only NMR blog that anyone cares to read. His blog is at http://blog.tenderbutton.com/?cat=9.

NMR Post-Processing Software for Mac Users

Phillip Grandinetti of Ohio State University (Research Group Site) offers an NMR post processing program for mac users called RMN at his website. He has an alpha version that runs under OS X and he is looking for alpha-testers to kick the tires. A more mature version is available that runs under Mac Classic OS.

 Mestrec laboratories also offer a cheap (50/100 Euro) software package that is available at iNMR.

May 22, 2006

AMMRL Meeting at 47th ENC - Asilomar, CA, April 2006 - Presentations

The AMMRL (Association of Managers in Magnetic Resonance Laboratories) held an annual meeting at which a number of presentations were given that give an idea of the economics and issues that arise for University NMR Facility Managers and Administrators, the links are below:
Charlie Fry—Introduction
Ken Visscher—Open-Access Laboratories in Industry    
Nick Burlinson—Design and Installation of a Departmental NMR Facility
Eugene DeRose—Problems and Protections for Pumped Magnets   
Josh Kurutz—A Survey of Business Models for Academic Facilities  
David Vander Velde—Cryoprobes and Money (a.k.a. Losing Money) 
Klaas Hallenga—Practical Tips and Tricks with Cryogenic Probes

The AMMRL has a website with some basic information at http://chemnmr.colorado.edu/ammrl/ and has an invaluable archive of “user group” e-mails that discuss all aspects of running and maintaining an NMR facility (Email – Archives 1993-Present). If you have a question about instrument problems, instrument and cryogen maintenance, user training, user competency, safety issues, etc …. chances are the answers are already included in this database. The database can also be searched by key word to arrive at “on-topic” material.

The Anatomy of a Superconducting NMR Magnet

May 18th, 2006

Dr Joseph Vaughn of Florida State University has placed an autopsy of a Varian R2D2 7.05 Tesla NMR magnet on the department website. The innards of the magnet and probe are all exposed in the gory photographs. Check it out at the FSU chemistry site : http://www.chem.fsu.edu/facilities/cutaway_nmr_magnet.asp

This is one of the siblings of the magnets that we operate in our labortory at Process NMR Associates. The site is only for those with a strong stomach.

8th International Bologna Conference on Magnetic Resonance in Porous Media

May 16th, 2006

This conference (MRPM8) will be held September 10-14 at the University of Bologna, Italy. It is being held a few days after the 6th Colloquium on Mobile magnetic Resonance in Aachen Germany, (September 6-8, CMMR6) to facilitate the attendance of conferees at both meetings.

Symbion Systems Inc

May 3rd, 2006

Symbion Systems Inc has developed a family of software products that provide a common interface for communicating with, networking, and controlling many analytical instruments, and sample systems, in a laboratory or process analysis setting. The software can control many individual analyzers from different vendors, process the data and visualize it, store the data in SQL databases, and perform complex chemometric analysis by calling various calibrations from many chemometric software platforms. The predictions obtained from process analytical instrumentation can be plotted, visualized, stored, and outputted under many standard formats for integration with process control and optimization software. A version can be obtained that is GLP/GMP/21 CFR, Part 11 compliant. The software will provide an excellent platform for development and execution of analytical laboratory methods, as well as process analytical applications.

One Moon Scientific Inc.

May 3rd, 2006

Bruce Johnson of One Moon Scientific (ex Merck) has produced a series of software tools for visualizing and analyzing spectroscopic data with particular emphasis on NMR data. His NMRViewJ can process and visualize NMR datasets in 1 or multiple dimensions and has built in molecular visualization and statistical data analysis tools. The software is “free” but Bruce asks that if you download and use it you should pay a “support contract fee” in order to support the ongoing development of the NMR software products.

16th ISMAR 2007 - Website Posted

April 26th, 2006

The International Society of Magnetic Resonance announces the 16th Triennial Conference to be held at Kenting, Taiwan, October 14-19, 2007. Organized by the Taiwan Magnetic Resonance Society, Academia Sinica, Taiwan – Website is found at http://www.ismar2007.sinica.edu.tw/

Energy Information

April 1st, 2006

Here are a few excellent links to the energy situation in the 21st Century:

Energy Technologies for the Twenty-First Century
WEC - Survey of Energy Resources 2001

DOE - This Week in Petroleum
Energy Information Administration
Main Site

Modern Drug Discovery - NMR Articles

March 15th, 2006

ACS Publication “Modern Drug Discovery” – Available NMR Articles
Screening with NMR
NMR Spectroscopy Software – Molecular biologists can now use proton NMR data to elucidate protein structure.
NMR on Target
Ultracool NMR Technology – Cryoprobes
Looking for Quality

NMR of Silicones in Pharmaceutical Developments

March 14th, 2006

Dow Corning have published a small overview paper on manufacturing processes and development of silicones in pharmaceutical formulations. The paper includes characterization details by FT-IR and NMR.

The 6th Colloquium on Mobile Magnetic Resonance - Official Website now Posted

March 14th, 2006

The 6th Colloquium on Mobile Magnetic Resonance has now posted an official website to cover the meeting at http://www.cmmr.de/index.htm

PNA Talk - Dr Giammatteo to Present Sigma Xi Seminar at Quinnipiac University

March 13th, 2006

Hamden, Conn. – Dr. Paul J. Giammatteo, co-founder of Process NMR Associates, will present “Pulse, Acquire, Control: Ten Years of Online High-Resolution Nuclear Magnetic Resonance (NMR) in Refining, Petrochemical and Food Manufacturing” at 12 p.m. on Monday, March 27, in the Clarice L. Buckman Theater at Quinnipiac University.

The free lecture is open to the public and is part of Sigma XI Special Seminar Series.

From gasoline manufacturing to butter production, more than 140 online NMRs have been placed in manufacturing plants worldwide. Giammatteo will discuss installation and utilization of this technology, its application in the petroleum and petrochemical industries and the future in pharmaceuticals.

Giammatteo co-founded Process NMR Associates, based in Danbury, in 1997. He previously worked for Texaco for 17 years. Giammatteo received his doctorate in chemistry from Wesleyan University and has published and presented more than 30 papers.

For more information, contact James Kirby, associate professor of chemistry at Quinnipiac, at (203) 582-8275 or James.Kirby@quinnipiac.edu

NMR Applications in Food Quality

March 10th, 2006

Overview document on Belgian Science Policy as it pertains to the use of low and high field NMR in the quality control of food.

Quantification by 1H NMR of Fatty Acids and Their Derivatives – by G. Knothe – USDA

An incredible repository of NMR information related to 1H and 13C NMR of Fatty Acids and their derivatives is found at the Lipid Library.

What is Your Carbon Footprint?

March 10th, 2006

A handy calculator from BP allows you to calculate your impact on global warming – Carbon Calculator.

Heavy Oil and Bitumen Upgrading

March 10th, 2006

Bitumen from Canadian Oil Sands – The Worlds New Marginal Supply of Oil” – January 2006

Oil Sands: Alberta’s Opportunity to Become a Significant Oil Exporter” – by Fluor, February 2004.

National Center for Upgrading Technology – Conference on “Upgrading and Refining of Heavy Oil, Bitumen and Synthetic Crude Oil” – September 2006 – Details

Bitumen and Very Heavy Crude Upgrading Technology – A Review of Long Term R&D Opportunities” March 2004

Genoil demonstration of an upgraded bitumen – effects on TBP and other physical properties.

Fueling an Integrated Energy Future” – Energy Innovation Network, December 2004

Kearl Lake Bitumen Extraction Project

Historical Perspective of the Heavy Oil Resources of Utah

USGS - “Heavy Oil and Natural Bitumen-Strategic Petroleum Resources

Non-Conventional Hydrocarbons – Where and How Much

Energy Independence for North America Through Heavy Oil Upgrading – Presentation – same material but presented as a Paper

Alberta Energy Research Institute – Strategic Research Plan

Shell – Gasification in Heavy Oil Upgrading in Alberta

The Impact of Emerging Research Techniques on Exploitation and Refining Technology Development” John Shaw – University of Alberta

Alberta’s Oils Sands Opportunity

Jacobs Engineering – Oils Sands Production Presentation

Total – Tar Sands Production Presentation

Effect of Tar Sands on World Oil Supply – Imperial Oil

Association for the Study of Peak Oil & Gas

Alternative Fuels – An Energy technology Perspective – March 2005

Integration Opportunities for Coal/Oil Coprocessing With Existing Refineries

Oil Sands Supply Outlook – March 2004

Spatial Encoding Produces 2D-NMR in a Single Scan

March 9th, 2006

Ultrafast 2D NMR spectroscopy obtained in a single scan is described by Lucio Frydman of the Weizman Institutein his paper entitled “Single Scan 2D NMR

Metabonomics Overview - High Field 1H NMR in Metabolite Profiling

March 9th, 2006

Professor John Lindon (Metabometrix Ltd) provides an Overview of Metabonomics relating the role of high field 1H NMR in metabolite profiling in biofluids.

Polymer Chemistry Resource

March 1st, 2006

Beautiful site that gives overviews of most polymer chemistry systems.

DECRA-FID Processing to Obtain Quantitative NMR Data????

March 1st, 2006

A strange CPACT NMR project development – DECRA processing of FID data - this involves quantitative analysis of FID signals in order to avoid automated phasing routines – in our process NMR experience phasing is a critical issue in the reproducibility of online NMR data, however, it is not an unsurmountable problem that leads to the development of new processing techniques such as those described here. Robust, repeatable phasing algorithms can be developed and implemented.

The Oil Drum - Peak Oil Blog

March 1st, 2006

The Oil Drum is a blog dealing with the impending global problem of Peak Oil Production also called “Hubbert’s Peak” – or should we say Peak “Easy” Oil Production.
Other sites that cover this topic are: Peak Oil News, Peak Energy, Past Peak (A little bit anti-Bush), and Peak Oil.Org.

Fossil fuel developments in Oil Shale, Tar Sands, and Coal Liquifaction will have to replace the “Easy Oil”. At $70 per barrel these are all plausible but research and development dollars have to be allocated. Running the world on Corn production is not the way to go technologically even though it satisfies the farming lobby.

European Commision Report on Food Quality Sensors

March 1st, 2006

A short European Commision Report on “Food Quality Sensors” – includes spectroscopy (NMR, UV/Vis, NIR-Vis, Vis-Fluorescence, thermoraphy, acoustic impulse, electronic noses).

Cheddar Cheese Flavour - Chemistry and Sensory Perceptions

March 1st, 2006

An excellent review on the chemistry of cheddar cheese and the sensory perceptions that arise from that chemistry. Comprehensive Reviews in Food Science and Food Safety, Vol 2 (2003).

Time-Domain NMR of Lipid Mobility in Bread

March 1st, 2006

Low resolution 1H TD-NMR was utilized to determine the mobility and translational diffusion coefficients of lipids in a low moisture (glassy) bread. The mobility of the lipids was found to be independent of moisture content. Journal of Cereal Science (28) 1998, 147-155.

Solid-State 13C NMR of Meteors

March 1st, 2006

Solid-state 1H and 13C Nuclear Magnetic Resonance (NMR) Spectroscopic experiments on isolated meteoritic Insoluble Organic Matter (IOM) obtained from four different carbonaceous chondrite meteorites; a CR2 (EET92042), a CI1 (Orgueil), a CM2 (Murchison), and an undesignated rank 2 meteorite, Tagish Lake. Short overview web page of NMR investigations into the carbon chemistry of meteorites. Journal article on this subject in PDF can be found here.If you are interested in having your meteor materials analyzed by solid-state 13C NMR contact John Edwards at Process NMR Associates.

NMR in Industry - Review Papers Available

February 26th, 2006

Industrial Applications of Nuclear Magnetic Resonance

NMR in Process Control

Applications of NMR to Food and Model Systems in Process Engineering

Process NMR Spectrometry

Practical Applications of NMR in Civil Engineering

February 26th, 2006

Practical Applications of NMR in Civil Engineering.

NMR of Hydrocarbons - Online Papers Available

February 26th, 2006

Though we have been performing NMR analysis to accurately correlate 1H NMR spectra with physical and chemical properties of gasoline (distillation, octane numbers, benzene, aromatics, olefins, oxygenates, RVP, density) for over a decade, papers still appear in the literature to vindicate that NMR is a powerful tool in the gasoline testing arena. In a Fuel paper (Vol 83, 2004, 187-193) the Swinss Federal Laboratories for Materials Testing and Research demonstrate a integral ratio method was demonstrated to yield excellent results for many gasoline parameters of interest to the engineer.

Another strong proponent of NMR utilization in the study of petroleum hydrocarbons is G.S. Kapur of the Indian Oil Corporation. Here are a few of his papers:
1) “Analysis of Hydrocarbon mixtures by Diffusion Ordered Spectroscopy”, Fuel 79, 1347-51 (2000).
2)”The qualitative probing of hydrogen bond strength by diffusion-ordered NMR spectroscopy”, Tetrahedron Letters 41, 7181-7185 (2000).
3)“Unambigous Resolution of a-Methyl and a- Methylene Protons in 1H-NMR Spectra of Heavy Petroleum Fractions”, Energy Fuels 2005, 19, 508-511
4)”Simplification an assignment of proton and 2-dimensional hetero-correlated NMR spectra of petroleum fractions using gradient selected editing pulse sequences” Fuel 81 (2002) 883-892

A practical guide to PFG spin echo NMR for mixture analysis has been written by Brian Antelek of Eastman Kodak.

Characterization of Coke - Analytical Approach

February 25th, 2006

An RSC review paper (Catalysis Volume 17) on the Characterization of Coke (on catalyst surfaces) is presented at the RSC site. The review covers use of AES, IR, Raman, UV, NMR, XRD, SIMS, etc.

NMR and Porometry

February 25th, 2006

An excellent overview of NMR applied to porosity of technology materials is presented in the dissertation of Roland Valckenborg entitled “NMR of Porous Technology Materials” (Eindhoven University of Technology 2001).
Another excellent site covering a peculiar NMR application to porosity is the site for NMR Cryoporometry. In this one measures pore size distribution by freezing liquids in the pores and then monitoring melting temperatures by NMR - as the melting point is depressed for crystals of small size the melting point depression gives a measurement of the pore simension that the frozen liquid was in. This is a speciality of Dr. J.B.W. Webber at the University of Kent, UK.

High Resolution Flow NMR for Reaction and Process Monitoring

February 23rd, 2006

Where NMR will make an impact in the process monitroing arena is in reaction monitoring where it has huge advantages over optical spectrocopy due to the chemical resolution inherent in the spectrum. An excellent poster by Mailwald et al. presents flow NMR applied to reaction monitoring utilizing a superconducting NMR spectrometer.

Bayesian Analysis of NMR Data - Software Available

February 23rd, 2006

Professor Larry Bretthorst (Washington University at St Louis) has made available a Varian VNMR based software package for Bayesian analysis of NMR data. He also maintains a site on Bayesian probability theory.

 

Overview of Solid-State 29Si NMR Studies of Silicone Gasket Materials

February 18th, 2006

Silicon-29 NMR has a unique ability to probe the detailed solid state chemistry of silicone rubber materials. The chemical shift range of the various silicone chemistry groups spans 120 ppm (at 4.9T this equates to 4800 Hz). This is a large dispersion which allows all chemistry types to be readily observed. In these, studies, however, we have not attempted to identify every chemical type present. We have identified general chemical types and followed their relative concentration from one sample to the next. Both cross polarization and single pulse experiments were performed on magic angle spinning samples (a full explanation of these two complimentary experiments is given below). Optimal experimental conditions were initially obtained and all subsequent samples have been analyzed under identical conditions to facilitate an understanding of the spectral changes from a chemistry as well as molecular mobility standpoint. Set NMR experiment conditions were used because of the time consuming nature of these experiments which typically take around 12 hours for each of the cross polarization and single pulse experiments.

Experimental
At the present time samples are being run on a Varian UnityPlus-200 spectrometer operating at a 29Si frequency of 39.74 MHz. The probe was a Doty Scientific 7 mm Supersonic CP/MAS probe using zirconia and Kel-F end caps. For the single pulse NMR experiments a pi/6 pulse of 2 microseconds was used with a relaxation delay of 4 seconds to facilitate quicker acquisition.The 4 second relaxation delay was obatined from full T1-inversion recovery experiments. Gated proton decoupling was used during FID acquisition. For the cross polarization experiments full contact time array experiments were obtained on the initial samples submitted. Due to the mobility of the polymer backbone the optimum cross polarization contact time for the polymer backbone was around 15 ms with signal lasting until 50+ ms. However, the more rigid structures in the polymer – such as the silicates, had optimum contact times around 3-5 ms. As a compromise we chose a 6.4 ms contact time which yielded good signal sensitivity for both the polymer and silicate components. Cross polarization inversion recovery experiments yielded a short relaxation delay of 2 seconds. A 1H p/2 pulse of 4.6 ms was used along with gated proton decouplind during FID acquisition. For all samples the same experimental conditions have been maintained. MAS spinning speeds were around 7 kHz to avoid spinning side band coincidence on real signals. Also, to avoid MAS induced modulation of the contact-time, the variable amplitude cross-polarization contact pulse was used.

Silicone Chemistry Observed by NMR
The notation in use for silicone chemistry is M,D,T,Q (mono, di, tri and quaternary) denoting the oxygen substitution on the silicon atom. The polymer backbone itself is predominantly D i.e. [(SiO2(CH3)2]n which has a typical resonance frequency around –21 ppm. The termination of the polymer would be an M group (SiO(CH3)3) (found at +4 to +10 ppm) or MOH (SiO(CH3)2OH) (-10 to –15 ppm). Another area of interest in the spectrum is the –20 to –10 ppm region which is partially due to MOH but also due to D type silicon centers that are within 5 monomer units of a termination. Thus, if hydrolysis of the silicone backbone is occuring, this region will increase in intensity as one will now have more silicon centers close to termination points as well as more MOH terminations.

In some gaskets one observes small signals in the –60 to –70 ppm region which is due to T type silicone centers (SiO3(CH3))n, however this is usually not observed. The only other region where one observes signal is in the –80 to –120 ppm region of the spectrum. These silicon centers can only be Q1 (SiO(OH)3), Q2 (SiO2(OH)2), Q3 (Si(OSi)3(OH)) or Q4 (SiO4)types, as only silicons with 4 attached oxygens can appear in this region, any methyl substitution would cause these silicons to appear in the +10 to –70 ppm range of the spectrum. Of relevance to any discussions on silicone polymers it should be noted that Q1 is equivalent to M(OH)3 , Q2 is equivalent to D(OH)2 , Q3 is equivalent to TOH.

When one looks at the NMR experiments for the certain silicones one does not observe a resonance at +10 to +4 ppm. This indicates that the predominant polymer termination is MOH. Silicate is observed, however, it is not clear if this silicate is a filler for hydrogen bonding crosslinking or actual polymer Q4/Q3/Q2 sites of directly condensed silicates acting as bonded crosslinking agents.

SP-MAS NMR Experiments
In this experiment one quantitatively observes all silicon species in the system allowing a “bulk” silicon type distribution to be calculated. One observes a narrow resonance at –21 ppm which is due to the silicone polymer backbone (-O-Si(CH3)2-O-)n. Very little signal is observed in the –20 to –10 ppm region indicating that the polymer chains are quite long. In the –80 to –120 ppm region of the spectrum one observes silicon present in silicate that has been added as a cross-linking agent. The hydrogen bonding between the silicone polymer and the Si-OH groups of the silicate add structural integrity to the gasket. It is differences in the silicate silanol (Si-OH) chemistry that may account for changes in compressibility of the gasket during service. Thus, one will observe relative changes in the amount of 29Si signal observed in the –80 to –103 ppm and –10 to –23 ppm regions of the spectrum. This region is where Q3 (Si(OSi)3(OH)), Q2 (Si(OSi)2(OH)2), and Q1 (Si(OSi)(OH)3) groups are found.

Parameters Calculated:
Silicate Content  - %Si in silicate filler
Q4                     - %Si atoms in Q4 silicate – Si(OSi)4
Qn                      - %Si atoms in Qn silicate (Q1, Q2, Q3)
Q4/Qn Ratio       - Silanol (Si-OH) distribution
% Polymer          - %Si in D & MOH polymer units

Relative changes in these parameters can be utilized to interpret changes in silicon chemistry caused by coolant exposure and service.

CP-MAS NMR Experiments
This experiment warrants a detailed explanation as the results are not quantitative from a “bulk” silicon chemistry standpoint. The CPMAS experiment utilizes the strong NMR signal that can be generated from protons (H) in the sample. The experiment preferentially observes silicons that are in close proximity to H. However, mobility is also a “problem” in this experiment. The way the experiment works is that the protons in the sample are polarized initially and magnetization is transferred from the protons to the silicons via their dipole-dipole interaction (similar to the interaction between 2 bar magnets). This interaction weakens the further the H and Si are from each other, and also weakens if there is considerable molecular motion. In the case of these samples this means that in the silicate region of the spectrum one observes an enhancement of the signal due to Si-OH containing species. In the case of the silicone polymer, however, one observes an overall decrease in the signal at –21 ppm due to the –(O-Si(CH3)2-O-)n backbone due to its rapid segmental (rubbery) molecular motions. One observes a large signal (that is hardly observable in the SPMAS spectra) in the –5 to –20 ppm region. This is due to silicone silicons that are at or directly adjacent to crosslinking sites (where there could be a D-silicate bond, or polymer termination sites such as MOH. The fact that they are enhanced by the CP technique indicates that these termination proximate silicons are motionally restricted compared to the rest of the silicone backbone. They represent either strongly hydrogen-bonded regions or chemical crosslinks of the type (O2(CH3)2Si–O–Si-O–Silicate) where a defect in the silicone backbone has reacted with a silanol of the silicate filler to form a Si-O-Si bond. This experiment is very powerful when used to observe relative changes in Si-OH chemistry in the silicate region and relative mobility changes in the polymer backbone.

Parameters Calculated:
% polymer backbone                 - %Si in mobile silicone backbone
% restricted polymer backbone  - %Si in motionally restricted regions of the silicone backbone (D units in close proximity to cross-linking sites, termination sites (MOH) or adjacent to termination sites).
Silicate Content                          - %Si in silicate filler.
Q4                                             - %Si in Q4 silicate – Si(Osi)4
Qn                                             - %Si in Qn silicate (Q1, Q2, Q3)
Q4/Qn Ratio                              - relative change in silanol (Si-OH) distribution

As with the SP-MAS calculated parameters one can utilize these parameters to determine changes in silicon chemistry resulting from coolant exposure and service.

Table I
Summary of 29Si NMR Chemical Shift Regions

Chemical Shift

Region (ppm)         Silicon Species

+10 to +4              Polymer termination sites (SiO(CH3)3) M

-5 to –15               Polymer Termination Sites (SiO(CH3)2OH) MOH

-10 to -20             Motionally restricted silicone polymer. Cross-linked and H-bonded –(O-Si(CH3)2-O-)n D units within five monomer units of polymer termination

-21                       D Units – motionally unrestricted silicone –(O-Si(CH3)2-O-)n

-75 to -85            Q1 Si(OSi)(OH)3 Silicate Center (M(OH)3)

-85 to -94            Q2 Si(OSi)2(OH)2 Silicate Center (D(OH)2)

-94 to -104         Q3 Si(OSi)3(OH) Silicate Center (TOH)

-104 to -120      Q4 Si(OSi)4 Silicate Center (Q)

Discussion
In use one observes that the gasket silicon chemistry changes dependent on additive chemistry and temperature/pressure conditions. When the polymers degrade one observes a general loss of D type signal intensity in the 29Si SP/MAS experiment as well as a corresponding increase in silicate content. One does not typically see changes in Q4 type but instead large changes in Q3 and Q2 content. These changes occur regardless of the presence of silicate in the coolant. This leads one to deduce that the Q3 and Q2 types are being generated by degradation of the polymer itself rather than a change in the chemistry of the silicate that was present in the sample initially. The author is not privy to additives and experimental conditions so he cannot speculate on the effect of silicate and other additives on the speed of the degradation that occurs. At the same time that Q3 and Q2 types are increasing in intensity the CP/MAS experiment clearly shows that there is a large increase in the relative amount MOH types and D types close to terminations (-5 to –20 ppm region). This proves that the exposure to coolants causes a hydrolysis of the Si-O-Si bond. However, it should also be notes that for the Q3 and Q2 types to appear one must also be hydrolyzing the Si-CH3 bonds.

The complimentary nature of the SP/MAS and CP/MAS experiments along with the use of only on set of experimental CP/MAS conditions means that relative changes in the various silicon chemistries can be analyzed to quantify the degree of degradation that a polymer has gone through.

Excellent Silicone Chemistry Link – Silicones in Pharmacutical Applications
For more information on this topic please contact:

John Edwards
Manager, Process and Analytical NMR Services
Process NMR Associates LLC,
87A Sand Pit Rd
Danbury, CT 06810, USA
Tel: (203) 744-5905

 

High Temperature Simulated Distillation in Petroleum Characterization

February 16th, 2006

High Temperature Simulated Distillation” by Dan Villalanti et al. in Encyclopedia of Analytical Chemistry, “Yield Correlations between Crude Assay Distillation and High Temperature Simulated Distillation” by Villalanti et al., and “Refinery Analytical Techniques Optimize Unit Performance” . All discuss the panacea of developing rapid HTSD as a suitable replacement for the very lengthy crude assay distillation.

Exxon Technology Reviews

February 15th, 2006

Residue Upgrading Technologies are discussed in severla papers including one presented in India, and another at ERTC 2004 in Prague In Moscow at the 1st Bottom of the Barrel Technology Conference a paper was presented on “Delivering Value for Resid and Heavy Feed“.

Trends in NMR Logging - Schlumberger Review Article

February 15th, 2006

Oil exploration companies are using NMR measurements in a number of downhole applications, such as characterizing formation fluids during reservoir evaluation and assessing formation producibility. In their article “Trends in NMR Logging” Schlumberger describe how NMR technology is changing the way reservoirs are designed, developed and managed. A similar paper, “Advances in NMR Logging” is presented by Robert freedman of Schlumberger.
Another review was produced in 1995, and “How to Use Borehole Nuclear Magnetic Resonance” was produced in 1997.

NMR Petrophysics offers NMR logging courses and provide NMR log analysis services.

A paper on the effect of sorbed oil on 1H NMR response was published byStanford University researchers.

A book is available on the subject entitled, “NMR Logging – Principles and Applications

Oil-Viscosity Predictions From Low-Field NMR Measurements” by J. Bryan and A. Kantzas, U. of Calgary/Tomographic Imaging and Porous Media Laboratory, and C. Bellehumeur, U. of Calgary

Application of TD-NMR in Civil Engineering

February 15th, 2006

Practical Applications of NMR in Civil Engineering by Bernd Wolter, Frédéric Kohl, Nina Surkowa, Gerd Dobmann
Fraunhofer-Institut fuer zerstoerungsfreie Pruefverfahren (IZFP), Saarbruecken, Germany

Book Chapter - Monitoring Thermal Processes by NMR Technology

February 15th, 2006

A neew book on Emerging Technologies for Food Processing has been published by Elsevier, edited by professor Da-Wen Sun ( National University of Ireland, Dublin) and has contribution from KVL Quality & Technology: Monitoring Thermal Processes by NMR Technology by Nanna Viereck, Marianne Dyrby and Søren B. Engelsen. (Oct 2005)

MathNMR - NYU Software for Spin and Spatial Tensor Manipulations

February 15th, 2006

Professor Alexej Jerschow has made available a Mathematica package that allows calculation of spin and spatial tensors – it is available at the following link : MathNMR.

Also available at this site are a very handy palm utility that lists frequencies, gyromagnetic ratios, natural abundances, receptivities, magnetic and quadrupolar moments, and reference compounds of most NMR active nuclei – download PalmNMR. He also provides a nicely designed interactive NMR frequency map.

Italian patent - New Pre-Saturation Methodology - PERFIDI

February 15th, 2006

Stanislav Sykora, in his NMR blog describes a recent patent applied for by himself and Paola Fantazzini, under the auspices of the University of Bologna. The patent surrounds a new pulse sequence that will allow selective excitation of components of a complex mixture based on the T1 relaxation differences between the NMR active nuclei in the components. The pulse sequence pre-amble is called PERFIDI. The Italian patent (#BO2005A000445 of July 01, 2005) is currently confidential but the invcentors have set up a website for potential licensors of the technology. The website includes a brief overview of the patent.

NMR Spin Splittings and Chemical Shift Tutorials - NMR Chemical Shift Predictor

February 15th, 2006

The Chemistry Department at the University of Saint Thomas, St Paul, MN, has an excellent number of tutorials covering the prediction of NMR spectra as well as a 1H NMR predictor web page.

 

NMR Structural Elucidation of Mountain Dew Nailed

February 13th, 2006

Ken Skidmore at San Francisco State University has finally answered the question on our lips for about a decade now….can NMR do the dew? Seems that it can, in an incredible turn of events the syrup formula has finally been exposed for what it really is… a $%!* load of sugar – the NMR evidence is irrefutable.

BioNMR Forum

February 9th, 2006

BioNMR is a forum for NMR spectroscopists to discuss their projects and find help from the online NMR community.

An excellent NMR users group exists (AMMRL-Association of Managers in Magnetic Resonance Laboratories) which consists of NMR facility managers and industrial NMR users. The group has an archive of questions posed and answers given to many issues that arise from the operation of Varian, Bruker and JEOL spectrometers predominantly in a college setting. Issues with NMR operation such as safety and peripheral infrastructure, as well as scheduling of users, manipulation of data and servicing of equipment are all covered in the discussions. Both groups can be joined at the sites above.

There is a Bruker users group archive directory located at http://calmarc3.cchem.berkeley.edu/archives/bum/. Membership of the Bruker users group can be obtaied by contacting he following e-mail (‘bruker-users-mail-request@purcell.cchem.berkeley.edu’). Membership to the Bruker brotherhood is carefully guarded and you will only be admitted if you operate Bruker equipment.

Free NMR Postprocessing Software - SpinWorks

February 9th, 2006

Dr. Kirk Marat at University of Manitoba has developed (and continues to develop) and excellent NMR processing freeware package that works very intuitively and well.

The FTP link to download the software is: ftp://davinci.chem.umanitoba.ca/pub/marat/SpinWorks/.

The current version is 2.5.3. There is also an excellent documentation PDF file to help users work through the program functionality.

This is how Dr Marat describes his software on his home page:

“What is SpinWorks
SpinWorks has two functions: The first is to provide easy basic off-line processing of 1D NMR and 2D data on personal computers. SpinWorks other function is the simulation and iterative analysis of complex second order spectra including dynamic NMR problems and certain solid-state NMR problems, in a manner similar to our UNIX Xsim program. SpinWorks 2.4 is the forth release of SpinWorks version to contain 2D processing. Full support is included for Bruker (XwinNMR/UXNMR) and Varian (Unix VNMR) data formats. Included F1 detection modes include States, TPPI, States-TPPI, Single Detection (QF), and echo-antiecho. There have also been some improvements and bug fixes in the 1D and simulation routines, and these should be at least as stable as those in version 1.3. While the program is to the point where it should (I hope) be useful, there will, no doubt, be bugs and there are things that don’t yet work. The aim of the program is to make a program easy enough for undergrads to process magnitude COSY spectra (for example) with a single mouse click, and yet still be flexible enough for research use. SpinWorks currently handles only one data set at a time. However, most new computers have sufficient memory to run two or three copies of SpinWorks simultaneously. This can be very useful when examining the rows and columns of a 2D data set.

Computer Requirements
SpinWorks requires a 486 or higher processor (Pentium recommended) running Windows 95, 98, NT 4.0, Windows 2000 Pro, or XP (NT 4.0, XP or Win 2000 recommended). Windows ME is probably O.K., but is untested. Installation currently requires about 5 Mbytes of disk space exclusive of NMR data. 32 Mbytes or more of RAM are recommended, depending on NMR data set and simulation sizes. SVGA 800 x 600 or better display required (1024×768 or better recommended). For 2D processing a Pentium class processor with 64 Mbytes of memory is the practical minimum. For 2D you should also have your display set to at least 16 bit colour, otherwise the image and contour level colours will be strange. I have received reports (but have not confirmed) that SpinWorks will run under Linux with the WINE package and on a Mac with SoftWindows. A three-button mouse is ideal, but SpinWorks will work just fine with a two-button mouse. Note that on “Wheel Mice” the mouse wheel also serves as the middle mouse button. The mouse wheel can also be used for vertical scaling of 1D spectra.”

 

Olive Oil Regional Authenticity from NMR Spectroscopy

February 8th, 2006

High field 1H and 13C NMR has been used to identify the region where an olive oil was produced – See Segre et al. Other methodologies have involved reacting hydroxyl groups in the olive oil with phospochloridite which allows detailed 31P NMR signatures to be obtained that reveal detailed chemistry distributions within the olive oil allowing an even greater discernment of chemical differences based on origin. Much of the work in this area has been performed by Apostolos Spyros in Crete. Here are a few of his papers:

“Application of 31P-NMR spectroscopy in food analysis. I. Quantitative determination of mono- and diglycerides in virgin olive oils”. A. Spyros, Photis Dais, J. Agric. Food Chem., 2000, 48, 802 . (pdf)

“Quantitative determination of the distribution of free hydroxylic and carboxylic groups in unsaturated polyester and alkyd resins by 31P NMR spectroscopy”.A. Spyros, J. Appl. Polym. Sci., 2002, 83, 1635. (pdf)
“Kinetics of diglyceride formation and isomerization in virgin olive oils by employing 31P NMR spectroscopy. Formulation of a quantitative measure to assess olive oil storage history”. A. Spyros, A. Fillipidis and P. Dais, J. Agric. Food Chem., 2004, 52, 157. (pdf)

This approach has also been applied to other edible oils so that their presence as adulterants can be observed and quantified:

“Classification of edible oils by employing 31P and 1H NMR Spectroscopy in combination with multivariate statistical analysis. A proposal for the detection of seed oil adulteration in virgin olive oils “. G. Vigli, A. Fillipidis, A. Spyros and P. Dais, J. Agric. Food Chem., 2003, 51, 5715. (pdf)
“Detection of extra virgin olive oil adulteration with lampante olive oil and refined olive oil using NMR spectroscopy and multivariate statistical analysis”. G. Fragaki, A. Spyros, G. Siragakis, E. Salivaras, P. Dais, J. Agric. Food. Chem., 2005, 53, 2810.(pdf)

Please contact Process NMR Associates with your potential 31P analysis.

More on NMR of Wine from Physics in Action

February 8th, 2006

Magnetic resonance sniffs out bad wine
Physics in Action: November 1998, Claude Guillou and Fabiano Reniero

Nuclear magnetic resonance (NMR) has come a long way since it was discovered in the 1940s. This physical phenomenon, which arises from the intrinsic spin possessed by many nuclei, has provided a better understanding of the physics of nuclei and molecules. It has also been exploited to analyse the properties of many different materials in chemistry, physics, polymer science and biomedicine.

Recent developments in the use of high magnetic fields and pulsed NMR techniques have made it possible to probe the structure of organic compounds as complex as proteins. Imaging machines based on the NMR principle have also been developed, and now provide a powerful and non-invasive tool for diagnosing a variety of medical conditions. However, less well known are the applications of NMR for analysing food and drink. At the Joint Research Centre at Ispra, we are using a technique to detect whether a wine has been adulterated with foreign substances. This method is based on an NMR measurement of the deuterium content of wine.

Nuclear magnetic resonance is observed for nuclei with non-zero nuclear spin, which includes both the hydrogen nucleus (a proton) and the deuterium nucleus (a proton and a neutron). However, the physical properties of these two isotopes dictate that the NMR signal produced by deuterium nuclei is over 100 times weaker than that produced by the same number of hydrogen nuclei. The natural abundance of deuterium is also extremely low, with typical samples of hydrogen containing only about 0.015% of deuterium. This means that the NMR signal due to deuterium in a natural sample containing hydrogen is about a million times weaker than the signal due to hydrogen.

Despite this drawback, deuterium has very interesting properties for quantitative NMR. Deuterium has a quadrupole magnetic moment rather than a dipole moment, which means that it is unaffected by the nuclear Overhauser effect. This effect – in which radiofrequency radiation applied to the nucleus changes the strength of the resonance – is often exploited to enhance the NMR signal, but it also degrades the precision of quantitative techniques. Indeed, deuterium spectra generally show distinct peaks that are suitable for quantitative purposes.

An important advantage of NMR is that the deuterium content can be determined for each of the sites in a hydrogen-containing molecule that are not magnetically equivalent. For ethanol, for example, it is possible to determine separately the deuterium content of the methyl group (CH2D) and the methylene alcohol group (CHD) in the deuterium NMR spectrum. The low natural abundance of deuterium means that it is only necessary to consider molecules containing a single deuterium atom.

How does the deuterium content of wine indicate whether it has been adulterated? This is possible because the deuterium content of water in the hydrosphere and biosphere is not a constant. As an extreme example, ice at the South Pole has very low deuterium content, with a deuterium-to-hydrogen ratio of about 90 parts per million (ppm), while ocean water has a value of about 156 ppm. This natural variation is due to thermodynamic and kinetic effects that take place during the water cycle, when water evaporates from the ocean and precipitates over land. The transpiration of water from plants also favours lighter isotopes, leading to a greater abundance of deuterium in the water contained in plants.

The deuterium content of the water in any plant, including the vines used in wine production, therefore depends on several factors that can be related to the geoclimatic conditions during plant growth. Moreover, the water in the plant is used in the photosynthesis of different chemicals, in particular the production of glucose. This transfers the isotopic content of the water to the glucose and other sugars present in the plant, which means that both the metabolism and physiology of the plant influence the final deuterium content of the sugars. The deuterium content of the sugars therefore provides a good indication of their botanical origin.

Although sugars are particularly difficult to study with deuterium NMR, it is possible to detect the deuterium content of the methyl group in ethanol, which is produced during the yeast fermentation of wine. Ethanol is responsible for most of the alcoholic content of wine, and it retains a deuterium-to-hydrogen ratio representative of the sugars from which it is produced. Quantitative NMR can therefore be used to determine whether the ethanol present in wine originates from the sugars naturally present in the grapes or whether other sugars have been added to boost the alcoholic content. This practice – known in the trade as “chaptalization” – is allowed in the European Union, but only within specified limits.

A simple way of using NMR to detect sugar in wine is to compare the deuterium content of the wine being tested with a genuine wine from the same geographical origin. This requires an accurate determination of the NMR signal from the genuine wine, which is being done for all European wine-producing countries by our laboratory and other official laboratories of the European Union. The NMR data of more than 10 000 samples, together with an exhaustive description of the wines, have been collated since 1991 and now provide a powerful tool against fraudulent practice.

Other isotopic indicators, such as the content of oxygen-18 in wine or carbon-13 in ethanol, can be used to help detect other types of fraud, such as watering down the wine or false declarations of geographic origin. These parameters are usually measured by mass spectrometry, but this does not provide the site-specific information given by deuterium NMR.

Isotopic techniques, particularly the NMR analysis of deuterium, can also be used to control the authenticity of fruit juices by first converting the sugars into ethanol using controlled fermentation. Deuterium NMR can also be used to characterize the origin of natural flavours such as vanillin or raspberry. In future the combination of nuclear magnetic resonance and mass spectrometry will almost certainly lead to many other applications in detecting frauds in food.

About the author
Claude Guillou and Fabiano Reniero are at the Joint Research Centre of the European Commission, Ispra, Italy.

NMR Method Patented to Determine Presence of Organic Sub-Structures in Molecules

February 8th, 2006

Bristol-Myers Squibb researchers have patented a methodology to determine the presence of particular molecular substructures in compounds by PCA analysis of NMR spectroscopy data. This analysis is performed on entire spectra or particular regions defined by the substructures of interest. US Patent 6,895,340

Ex-Situ NMR available for license from Berkley Lab

February 8th, 2006

Ex-situ NMR (US Patent 6,652,833) is currently available for license from the Lawrence Berkely Lab. This NMR analysis is described in a paper presented in Physique and in the following Science article (“High-Resolution NMR Spectroscopy with a Portable Single-Sided Sensor” by J. Perlo, V. Demas, F. Casanova, C. A. Meriles, J. Reimer, A. Pines, and B. Blumich (2005). Science 308: 1279-1279

Spoilage of Wine observed by NMR of Intact Bottles

February 8th, 2006

A large bore superconducting magnet and specialized probe is all that is required to check that your $4500 bottle of Mouton Rothschild 1865 is not a extraordinarily expensive bottle of vinegar US Patent 6,911,822.

Patented NMR Method for Quality Control of Medicinal Natural Products

February 8th, 2006

Pattern recognition technology in conjunction with 1H and 13C NMR spectroscopy is used to determine the standard specification expected for medicinal grade natural products – see US Patent 6,806,090

Food Authentification by SNIF-NMR

February 8th, 2006

Gérard Martin of Eurofins Scientific, CNRS, Nantes University, Nantes – France, writes:
” Methodology: No dramatic improvement in NMR instrumentation originated during the last decade where an 11.4 T spectrometer, fitted with dedicated 2H{1H} probe and a 19F locking canal represents a good compromise between cost and efficiency. Since the main challenge for 2H-SNIF-NMR is to overcome its low sensitivity, efforts were directed in this way. The cheapest solution is to avoid the use of an internal reference that spares room in the cell for more molecules of interest and this can be done in two ways. First, the isotope ratios may be computed from the molar ratios of the deuterium isotopomeres, and the overall (D/H) value measured by Mass Spectrometry (IRMS). An alternative is to replace the chemical reference by an electronic signal conveniently generated (ERETIC method).

Wines and juices: Since 1991, the European data bank on wines has been established years after years and contains now the isotopic data of several thousands of wines from the main producing countries in Europe. Illegal enrichment of wines can be checked out and, according to the pertinence of the data bank, geographic origins of QWPSR wines can be controlled. Private ventures took also an interest in building up specific databanks of wines from third countries. The market of fruit juices has been stabilized by SNIF-NMR and the quantity of sucrose added in pure juices has been severely reduced. A joint approach using SNIF-NMR and IRMS is very useful for fighting against other sophisticated frauds.

Aromas and perfumes: The replacement of vanillin from beans (Vanilla Planifolia) by synthetic vanillin is an old practice and during thirty years, isotopic methods (IRMS and SNIF-NMR) were a nightmare to the fraudsters. Biotechnology forms the subject of the last serial of the vanillin saga: vanillin obtained from ferrulic acid by fermentation has been declared “natural” providing that all the steps and ingredients taking part in its manufacture are “natural”. The potentiality of isotopic analysis for solving the problem of the natural status of biotechnological vanillin will be discussed. Progresses in the authentication of aromatic molecules obtained from the shikimate pathway and of monoterpenes bio synthesized according to the deoxyxylulose pathway are also pointed out.

Miscellaneous applications of SNIF-NMR: During the last decade, fats and oils, fishes, dairy products and coffees received a great attention form the official and private laboratories in charge of the consumer protection. Legal (tobacco) and illegal (heroin) drugs have also been authenticated by SNIF-NMR.”

See also – Eurofins Site, and the following papers in The Chemical Educator (Elsevier), and this US Customs Service Report, explain the technique and a simple application very well.

SNIF NMR methodology has actually been patented US Patent 6,815,213, US Patent 4,550,082.

See Process NMR Associates for your NMR analysis needs.

13C NMR Analysis for Authentification of Gum Arabic

February 8th, 2006

35 samples of Gum Arabic (acacia senegal) were analyzed by 13C NMR spectroscopy and the “average 13C NMR peak relative intensities” were calculated. This average 13C NMR signature can be used to determine the authenticity of a gum arabis sample and allows for observation of adulterants which are typically gums from other tropical trees (eg. gum talha (Acacia Seyal), Combretum, etc.). 13C NMR has been suggested as a specification of Gum Arabic quality in the following paper:
“Gum arabic (Acacia senegal): unambiguous identification by 13C-NMR spectroscopy as an adjunct to the Revised JECFA Specification, and the application of 13C-NMR spectra for regulatory/legislative purposes.” by Anderson DM, Millar JR, Weiping W., Chemistry Department, University, Edinburgh, UK. Published in Food Additives and Contaminants, 1991 Jul-Aug;8(4):405-21

See Process NMR Associates for your 13c analysis needs.

NMR Database - Essential Oils and Carrier Oils

February 7th, 2006

PNA has created and extensive NMR database comprising 160+ Essential Oils and 40+ Fixed Oils.
Process NMR Associates is interested in developing a comprehensive database of NMR data that can be correlated to GC/GCMS data.
If you have essential oils that have GC or GCMS data associated with them, we would be happy to provide you with a free 1H/13C analysis in exchange for
including your EO and analytical data into the current database. Contact John Edwards if you are interested.
The database includes 1H and 13C NMR spectra of the following oils:

Essential Oils
Ajowan EO Trachyspermum copticum – India (seed)
Allspice Berry EO Pimenta officinalis
Amyris EO Amyris Balsamifera – Jamaica
Angelica Root EO Angelica archangelica
Angelica Seed EO Angelica archangelica
Anise Seed EO Pimpinella anisum
Armoise EO Artemesia herba alba – Morocco
Balsam Peru EO Myroxylon balsamum
Balsam Tolu EO Myroxylon balsamum – El Salvador
Basil EO Ocimum basilicum
Bay Leaf EO Pimenta racemosa
Bay Laurel EO Laurus nobilus – Jamaica
Benzoin Liquid Resin Benzion Styrax – China
Bergamot EO Citrus bergamia
Birch Sweet EO Betula lenta
Black Pepper EO Piper nigrum – India
Blood Orange EO Citrus sinensis var.
Bog Myrtle EO Myrica gale – Europe
Cabrueva EO Myocarpus fastigiatus – South America
Cade EO Juniperus oxycedrus – Spain
Cajeput EO Melaleuca cajeputi
Calamus EO Acorus calamus
Camphor EO Cinnamomum camphora
Cananga EO Cananga odorata
Caraway Seed EO Carum carvi
Cardamom Seed EO Elattaria cardamomum
Cassia EO Cinnamomum Cassia – China
Catnip EO Nepeta cataria
Carrot Seed EO Daucus carota
Cedarwood EO Cedrus atlantica
Cedarwood Atlas EO Cedrus atlantica – Morocco
Cedarwood Chinese EO - Cupressus funebris – China
Cedarwood Himalayan EO Cedrus deodara – Himalaya
Cedarwood Mexicana EO Juniperus mexicana – Mexico (also Texas Cedarwood)
Cedarwood Virginian EO Juniperus Virginiana – USA
Cedar Leaf EO Thuja occidentalis – USA
Celery Seed EO Apium graveolens
Chamomile German EO Matricaria chamomilla
Chamomile Egypt EO Matricaria chamomilla
Chamomile Spain EO Matricaria chamomilla
Chamomile Roman EO Anthemis nobilis
Cinnamon Bark EO Cinnamomum
Cinnamon Leaf EO Cinnamomum zeylanicum
Citronella EO Cymbopogon nardus
Citronella Sri Lanka EO Cymbopogon nardus
Citronella Java EO Cymbopogon winterianus
Clary Sage EO Salvia sclarea
Clove Bud EO Eugenia caryophyllata
Clove Leaf EO Eugenia caryophyllata – Madagascar
Copaiba Balsam EO Copaifera officinalis
Coriander Seed EO Coriandrum
Cumin EO Cumimum cymimum
Cypress EO Cypressus sempervirens
Cypriol EO Cyperus scariosus – Brazil (Flowers)
Davana EO Aretemesia pallens
Dill Seed EO Anethum sowa – India
Dill Weed EO Anethum graveolens
Dragons Blood EO Croton lechleri – South America (Resin)
Dwarf Pine EO Pinus mugo
Elemi EO Canarium luzonicum
Eucalyptus Citriodora EO Eucalyptus citriodora
Eucalyptus Globulus EO Eucalyptus globulus
Eucalyptus Radiata EO Eucalyptus radiata
Eucalyptus Spain EO Eucalyptus globulus
Eucalyptus China EO Eucalyptus globulus
Eucalyptus Smithii EO Eucalyptus smithii – China (leaf)
Fennel Sweet EO Foeniculum vulgare
Fennel Hungary EO Foeniculum vulgare
Fennel Spain EO Foeniculum vulgare
Fennel Rectified EO Foeniculum vulgare
Fennel Sweet EO Foeniculum vulgare
Fir Needle EO Abies alba
Fir Siberian EO Abies sibirica – Austria (Needle)
Fir Canadian EO Abies balsamea – USA (Needle)
Frankincense EO Boswellia carteri
Galbanum EO Ferula galbaniflua – Turkey (Gum)
Garlic EO Allium sativum – Mexico (Bulb)
Geranium EO Pelargonium graveolens
Geranium Rose EO Pelargonium roseum – France
Ginger EO Zingiber officinale
Ginger Grass EO Cymbopogon martini – China
Grapefruit Pink EO Citrus paradise
Guaiacwood EO Bulnesia sarmienti – Paraguay
Helichrysum EO Helichrysum angustifolium
Helichrysum Italicum EO Helichrysum italicum
Hop EO Humulus lupulus
Hyssop EO Hyssopus officinalis
Juniper Berry EO Juniperus communis
Labdanum EO Cistus labdanum
Lantane EO Lantara camara – Madagascar
Lavandin EO Lavendula latifolia
Lavender EO Lavendula angustifolia
Lemon EO Citrus limon
Lemongrass EO Cymbopogon citratus
Lemon Myrtle EO Backhousia citriodora – Australia
Lime EO Citrus aurantium
Lime (Distilled) EO Citrus aurantifolia
Lime (Cold Pressed) EO Citrus aurantifolia
Litsea Cubeba EO Litsea cubeba – China
Mace EO Myristica fragrans – Spain (Husk)
Mandarin EO Citrus reticulata
Marjoram EO Origanum majorana
Melissa EO (Lemon Balm) Melissa officinalis
Mint Brazil EO Mentha arvensis
Mint China EO Mentha arvensis
Mint Japan EO Mentha arvensis
Mugwort EO Artemisia vulgaris
Mullein EO Verbascum thapsus – India (Leaf)
Myrrh EO Commiphora myrrha
Myrtle EO Myrtus communis
Neroli EO Citrus Aurantium – Egypt
Niaouli (Cineole) EO Melaleuca viridiflora
Niaouli (Nerolidol) EO Melaleuca quinquinervia
Nutmeg EO Myristica fragrans
Oat EO Avena sativa
Opoponax EO Commiphora guidotti – Ethiopia
Orange Bitter EO Citrus aurantium
Orange Sweet EO Citrus sinensis
Oregano EO Thymus capitatus
Palmarosa EO Cymbopogon martini
Parsley Seed EO Petroselinum sativum
Patchouli EO Pogostemon cablin
Pennyroyal EO Mentha pulegium
Pepper Black EO Piper nigrum
Peppermint EO Mentha piperita
Petitgrain EO Citrus aurantium
Pine Needle EO Abies sibirica
Pine Dwarf EO Pinus mugo – Austria (Needle)
Pine Scots EO Pinus sylvestris – Hungary (Needle Twig)
Pine EO Pinus pinaster – USA (Needle)
Ravensara EO Ravensara aromatica
Rosalina EO Melaleuca ericifolia – Australia
Rose EO Rosa centifolia
Rosemary EO Rosmarinus officinalis
Rosewood EO Aniba roseaodora
Sage EO Salvia officinalis
Sandalwood EO ( Mysore ) Santalum album
Spearmint EO Mentha spicata
Spike Lavender EO Lavandula latifolia
Spikenard EO Nardostachys jatamansi
Spruce EO Tsuga canadensis
Spruce Black EO Picea mariana – Norway (Needle)
Star Anise EO Illicium verum
Tagetes EO Tagetes minuta
Tangerine EO Citrus reticulata
Tarragon EO Dracunculus spp.
Tea Tree EO Melaleuca alternifolia
Thuja EO Thuja occidentalis
Thyme Red EO Thymus vulgaris
Thyme Sweet EO Thymus vulgaris – France
Thyme White EO Thymus vulgaris – Spain
Turmeric EO Curcuma longa – India
Valerian Root EO Val ariana officinalis
Verbena EO Lippia citriodora
Vetiver EO Vetiveria zizanoides
Wintergreen EO Gaultheria procumben
Wormwood EO Artemisia absinthium
Yarrow EO Achillea Millefolium – Bulgaria
Ylang-Ylang Extra EO Canaga odorata
Ylang-Ylang I EO Canaga odorata
Ylang-Ylang III EO Canaga odorata

Carrier oils
Apricot Kernel Oil Prunus armeniaca
Aloe Vera Oil Aloe barbadensis -USA
Avocado Oil Persea americana
Borage Oil Borago officinalis
Camelina Oil Camelina sativa
Camellia Oil Camellia sinesis – Japan (Seed)
Canola Oil Brassica napus – Canada
Castor Oil Ricinus communis – India (Seed)
Coconut Oil (Fractionated) Cocos nucifera
Coconut Oil (Virgin) Cocos nucifera
Corn Oil
Cottonseed Oil Gossypium seminis – USA (Seed)
Emu Oil
Evening Primrose Oil Oenothers biennis
Flax Seed (Linseed) Oil Linum usitatissimum – USA
Foraha (Tamanu) Calophyllum Inophyllum
Grapeseed Oil Vitis vinifera
Hazelnut Oil Corylus avellana
Hemp Seed Oil Cannabis Sativa
Jojoba Golden Simmondsia chinensis
Kukui Oil Aleurites moluccans
Macadamia Nut Oil Macadamia integrifolia – Australia
Olive Oil Olea eurpaea – Italy
Palm Oil Passiflora elacsis – USA
Palm Kernel Oil Passiflora aincarnata – Malaysia
Peanut Oil Arachis hypogeae – USA
Pecan Oil Algooquian paccan – USA
Pistachio Nut Oil Pistacia vera – USA
Rose Hip Seed Oil Rosa mosqueta
Safflower Oil Carthamus tinctorius – Guatamala
Sesame Oil Sesamum indicum
Soya Bean Oil Soja hispida – USA
Sunflower Oil (High Oleic) Helianthus annuus
Sweet Almond Oil Prunus dulcis
Walnut Oil Juglans ragia – USA
Wheatgerm Oil Triticum vulgare
Almond Fragrance Oil
Bitter Almond Fragrance Oil
Coconut Fragrance Oil
Rosemary Oil Extract

NMR Reference: Ref: “Essential Oils Analysis by Capillary Gas Chromatography and Carbon-13 NMR Spectroscopy ”
by K.H. Kubeczka and V. Formacek, 2nd Ed, Wiley, NY (2002)

Essential Oil Chemistry Reference: Journal of Essential Oil Research

See Process NMR Associates Essential Oils Page

NMR Acronyms

February 7th, 2006

Excellent NMR Acronym Summary Pages –     Oxford University,  

                                                                    University of Wisconsin

NMR on a Chip

January 25th, 2006

All you need to purchase with this PCI Card NMR spectrometer is an amplifier, a magnet and probe. Details can be obtained at the Spincore RadioProcessor Page. Benchtop high resolution NMR is very close to being a reality. Combining new spectrometer design with micro-probe and sample automation such as that found at Protasis will make benchtop QA-QC spectrometers a reality and place NMR spectrometers in the hands of people who can utilize them for routine testing at an affordable price.

Fat Content of Live Salmon

January 25th, 2006

MOUSE NMR application on Salmon

Mobile NMR of Polyethylene Pipes

January 25th, 2006

MOUSE NMR application to polyethylene pipes.

Upcoming NMR Meetings for 2006

January 25th, 2006

47th ENC Conference will be held April 23 – 28, 2006, at The Asilomar Conference Center, Pacific Grove, California – Program.

EUROMAR - York will be held July 16-21, 2006 at The University of York Main Campus, Programme

22nd International Conferences on Magnetic Resonance in Biological Systems will be held August 20-25, 2006 in Goettingen, Germany – programme

6th Colloquium on Mobile NMR will be held 6-8 September 2006 in Aachen, Germany – Program

SMASH 2006 will be held September 10-13 at the Sheraton Hotel in Burlington, Vermont – Program

The NMR Symposium of the 48th Rocky Mountain Conference on Analytical Chemistry will be held July 23 – 27, 2006. The conference site is the Beaver Run Resort & Conference Center in Breckenridge, Colorado.

21st Meeting of the Central European NMR Discussion Groups will be held April 23-26, 2006, Valtice, Czech Republic in the hotel HUBERTUS in Valtice Castle

14th ISMRM will be held 6-12 May 2006 in Seattle Washington – program

ANZMAG 2006 will be held February 12-16 at the Murramarang National Park, NSW, Australia – Programme

Fast NMR Field Cycling

January 25th, 2006

Stelar s.r.l of Italy manufacture a fast field cycling NMR spectrometer that shuttles a sample in and out of a varying magnetic field to generate T1 longitudinal relaxation profiles obtained by measuring T1 at a series of different magnetic field strengths. Stelar has developed low-inductance, air-coil magnets and power supplies capable of switching the field electronically to any desired value in a matter of milliseconds while, at the same time, maintaining the high field stability and homogeneity required by NMR. This allows the link between NMR relaxation phenomena and molecular dynamics to explored initially in the following application fields: the hydration of paramagnetic metal ions and organometallic complexes, the dynamics of liquid crystals, and the dynamics of proteins.

Fast NMR Field Cycling

January 25th, 2006

Stelar s.r.l of Italy manufacture a fast field cycling NMR spectrometer that shuttles a sample in and out of a varying magnetic field to generate T1 longitudinal relaxation profiles obtained by measuring T1 at a series of different magnetic field strengths. Stelar has developed low-inductance, air-coil magnets and power supplies capable of switching the field electronically to any desired value in a matter of milliseconds while, at the same time, maintaining the high field stability and homogeneity required by NMR. This allows the link between NMR relaxation phenomena and molecular dynamics to explored initially in the following application fields: the hydration of paramagnetic metal ions and organometallic complexes, the dynamics of liquid crystals, and the dynamics of proteins.

Anatomy of a Process NMR Spectrometer

January 2nd, 2006

Online NMR with Open Enclosure

Open RF Components of NMR Spectrometer

Open RF Components_2

Shim Unit DACS

Open Magnet Enclosure – Fully Shielded NdFe Permanent Magnet at 1.4 Tesla

NCUT - Workshop Proceedings

December 28th, 2005

Final Report of the Oil Sands Chemistry and Engine Emissions Roadmap Workshop

Fuel Technical Reviews from ChevronTexaco

December 28th, 2005

Motor Gasoline Technical Review
Aviation Fuel Technical Review
Diesel Fuel technical Review

Challenges in the Development of New Processes for Refining and Petrochemistry

December 28th, 2005

Overview of challenges to be faced in developing new refining and petrochemical processes.

Government natioanl Renewable Energy Laboratory - Publications

December 28th, 2005

http://www.nrel.gov/publications/

Excellent Paper on Reaction Modeling Trends

December 28th, 2005

Reaction Modeling Trends – a paper by KBC

Low Sulfur Diesel

December 28th, 2005

Excellent review of the effect of the new low sulfur diesel EPA legislation on fuel supply and costs – DOE Report The entire low sulfur diesel report from DOE can be downloaded from here.
Also an excellent paper from Topsoe on revamping HDS units to meet the new specification.
Finally a Chevron technical review of diesel fuels.

IASC - NMR Methodology for Aloe Vera Certification

December 28th, 2005

The International Aloe Science Council has mandated that quantitative 1H NMR analysis be used to certify the quality of Aloe Vera products being sold or placed on the market. Attached here is an article on the subject as well as the certification details from IASC. An excerpt from the article states: “By means of NMR spectrum, it is possible to record all the essential components of Aloe vera and thus make a clear statement regarding the quality of the product. Impurities, be they natural or artificial, can be detected. Decomposition products give information about the period of time elapsing between the leaves being harvested and processed, or about the age of the raw material.”

Process NMR Associates has developed the NMR methodologies prescribed by IASC and can quantify Acemannan, glucose and Malic Acid in the presence of a Nicotinic Acid Amide Standard. Breakdown products such as acetic acid, lactic acid, pyruvic acid, succinic acid can be readily quantified as can the presence of additives such as citric and benzoic acids. Adulterants such as maltodextrin can be readily quantified and the presence of n0n-aloe vera products can also be determined.

Contact John Edwards for details.

Academics View of the NMR Marketplace

December 28th, 2005

Here is an article from Spectroscopy Magazine that typifies the view of NMR. NMR as a sensor for industrial control is still not a concept that readily springs to mind even with people intimately involved in NMR research.

New Russian TD-NMR Company

December 28th, 2005

Just found a new player in the TD-NMR spectrometer domain – Resonance Systems Ltd. They also have a blog. Appears to be a new system similar to Magritek technology as well as Minispec.

Fantastic Gift Ideas for The Person Who Has Everything

December 25th, 2005

My sister and brother-in-law opened my eyes to the socially conscious way to give gifts to people who already have more than they need. Who wouldn’t appreciate a gift that leads to the construction of a toilet in a Congo refugee camp? These cool, “make a difference” gifts can be bought online at Oxfamunwrapped.com. Here is my gift for Christmas…
Toilet constructed in Phillip, Democratic Republic of Congo

Mid-Hudson ACS - Planned March 2006 Meeting Schedule

December 22nd, 2005

Meeting #1
“Science Policy: Chemistry and Nuclear Waste Disposal” Dr. Douglas J. Raber GreenPoint Science
Wednesday, March 15, 2006, Orange County Community College Middletown, Refreshments: 6:15 PM, Lecture: 7:00 PM (Room TBA)* Room to be announced on the Mid-Hudson ACS listserv and at www.midhudsonacs.org. Contact Tim MacMahon (OCCC) at 845-341-4575 or by e-mail at tmacmaho@sunyorange.edu.

About the lecture: Soon after the end of World War II, peaceful uses of atomic energy became a major thrust of scientific endeavor around the world. At present, the world derives 16 percent of its electricity from nuclear power, mainly in industrialized countries. The level is 20 percent in the United States and 75 percent in France. Concerns about safety in the nuclear power industry have been a source of continuing controversy for many years, and the single most important challenge in this area is what to do with nuclear waste. The spent nuclear fuel from a reactor is highly radioactive and will remain so for an extremely long time. The potential for release of radioactive material into the environment is strongly coupled to the chemical properties of the waste material, so many of the problems and many of the potential solutions are chemical in nature. This talk will present issues in current national policy and will discuss the interplay between science and policy, using several National Research Council studies to illustrate the complexity of the problem. How is scientific input obtained? How is it utilized? Does it receive the respect that it deserves? And what can you do to improve the situation?

About the speaker: Dr. Raber is a science policy consultant with GreenPoint Science, which he formed in 2004. Previously, he served for thirteen years as Director and then Senior Scholar of the Board on Chemical Sciences and Technology at the National Academy of Sciences and its operating arm, the National Research Council (NRC). Before joining the NRC in 1989, he was a member of the faculty of the University of South Florida from 1970 to 1990, publishing some 70 research articles. Dr. Raber is active in ACS governance, serving recently on the C&EN Advisory Board, the Committee on Chemistry and Public Affairs, and the Committee on Science (which he previously chaired). He recently completed several terms as the Secretary of the U.S. National Committee for IUPAC and currently serves as Chair of the Chemical Technology Operating Council of the AIChE. Dr. Raber’s responsibilities at the NRC centered on organizing and directing science and science policy studies, particularly in the areas of federal policy and its interrelationships with the chemical sciences. These efforts resulted in more than 50 reports and monographs that provide technical policy guidance on topics that encompass R&D opportunities, laboratory safety and management, nuclear waste disposal, and the threat of terrorism.

Directions: From Rte. 17M West in Middletown turn left onto Fulton Street. Turn left onto Wawayanda Ave. Turn left onto Grandview Ave. Enter parking lot on right. For complete directions and campus map, visit http://www.sunyorange.edu/aboutus/directions/index.shtml.

Meeting #2
“Nanoscale Building Blocks for Mesoscopic Materials” Dr. Tom Mallouk, Pennsylvania State University, Monday, March 20, 2006, at IBM* Refreshments: 6:15 PM, Lecture: 7:00 PM

*Registration for this talk is required. Contact Charles Davis (IBM) at 845-892-9570 or by e-mail at cdavis@us.ibm.com by March 13. Photo ID must be presented at the site. Room information and directions will be provided to all registered attendees.

About the speaker: Dr. Mallouk is the DuPont Professor of Materials Chemistry and Physics and the Director of the Center for Nanoscale Science at Penn State. His research focuses on the assembly of nanoscale materials and their applications to interesting problems in chemistry, including photocatalysis, molecular electronics, environmental remediation, fuel cell electrochemistry, chemical sensing, and catalytically driven movement.

Meeting #3
“Mechanism of Oxidation of DNA by Pt(IV) Complexes” Dr. Sunhee Choi, Department of Chemistry and Biochemistry, Middlebury College
Friday, March 31 2006, Vassar College, Refreshments:6:15 PM, Lecture:7:00 PM Mudd Chemistry Building (Room TBA)*

*Room to be announced on the Mid-Hudson ACS listserv and at www.midhudsonacs.org.
Contact Joe Tanski (Vassar) at 845-437-7503 or by e-mail at jotanski@vassar.edu.

About the lecture: Platinum complexes are biologically important for their anticancer activities. The interaction of DNA with PtII complexes has been extensively studied by many research groups. PtIV complexes are kinetically inert and their reaction with DNA was not generally expected. However, Dr. Choi’s research has shown that PtIV complexes with highly electron-withdrawing and bulky ligands have high reduction potentials and high reactivity toward 5’-GMP. Furthermore, a PtIV complex, trans-Pt(d,l)(1,2-(NH2)2C6H10)Cl4, [PtIVCl4(dach)], which has a high reduction potential, oxidizes 5’-dGMP, 3’-dGMP and 5’-d[GTTTT]-3’. Kinetic studies and the proposed mechanism will be discussed.

About the speaker: Dr. Sunhee Choi is Professor of Chemistry and Biochemistry at Middlebury College in Vermont. Dr. Choi received a B.A. degree from Seoul National University in 1973 and went on to receive a master’s degree in Physical Chemistry at the Korean Advanced Institute of Science in 1975. She earned her Ph.D. in Physical Chemistry at Princeton University in 1982 in the laboratory of Professor Thomas G. Spiro. After her Ph.D. she became an industrial chemist at Colgate-Palmolive where she was awarded the Colgate Presidential Award for Technical Excellence and obtained a U.S. Patent for cold water detergency. In the fall of 1987, she joined the faculty at Middlebury. Dr. Choi is active in research in metals in biological system with many of her undergraduate colleagues. Her research has been funded from a variety of sources such as the National Institutes of Health, National Science Foundation, Petroleum Research Fund, Research Corporation, and Vermont-EPSCOR.

Directions: Vassar College is located off Raymond Avenue in Poughkeepsie, NY. Refer to the following link for driving directions and campus map: http://www.vassar.edu/directions/. Enter the Main Entrance of the campus on Raymond Avenue and The Main Building and College Center are in front of the Main Entrance. The Security Guard at the Main Entrance will direct you to parking. The Villard Room is on the second floor of the Main Building/College Center. The Alumnae House is located across the street from the tennis courts on Raymond Ave at Vassar.

John Edwards becomes Mid-Hudson ACS Chair-Elect

December 22nd, 2005

John Edwards has been voted in as Chair-Elect of the Mid-Hudson ACS Section.

Solid-State NMR and Polymorphism

December 1st, 2005

At PNA we have recently been working on some interesting polymorph projects utilizing solid-state 13C NMR. Excellent reviews of this subject are given at: Robin Harris of University of Durham (my alma mater) and Cardiff School of Chemistry
A good example of polymorphism determined by NMR in 4-azasteroid systems is given here….Morzycki et al…Steroids 67, 621 (2002).
The FDA have summarized the effects of polymorphism in pharmaceutical solids (PDF Version)

We perform these studies on a dedicated Varian UnityPlus-200 spectrometer to yield spectral and relaxation data to allow the determination of drug-excipient interactions, as well as simple polymorph differentiation and amorphous material content. Both 13C SP-MAS and CP-MAS experiments are utilized in these studies along with T1 and cross-relaxation time determinations.

See Process NMR Associates for your Polymorphism Analysis

NMR Capabilities Expanded at Process NMR Associates

November 16th, 2005

We have recently added TD-NMR capabilities to out suite of NMR services by acquiring Oxford Instruments spectrometers that perform TD-NMR at 2.5 and 20 MHz. The 20 MHz system is an 18 mm Oxford QP20 system, while the 2.5 MHz system is a custom spectrometer operating with a 50 mm bore magnet for large sample analysis. This will allow us to expand into commodities testing such as total hydrogen analysis, oil and water content analysis, and will also allow us to develop low field process NMR applications.

Process NMR Technology at CPACT

November 14th, 2005

A summary of process NMR projects undertaken by CPACT from 1998-2001 is shown on the CPACT website. It’s difficult to decipher why the projects did not come to fruition. Work on the projects appears to have ceased.

NMR and Spectroscopy Events in the Tri-State Area - November 2005

November 9th, 2005

Eastern Analytical Symposium will have a lot of NMR, PAT and spectroscopy sessions according to their technical session schedule. Paul Giammatteo of Process NMR Associates will present on Thursday November 17 – here are the details of his session –
Process Spectroscopy in Industry – Chemicals, Food and PAT, Arranged in Conjunction with the Delaware Valley Section of SAS
Chair, Lois Weyer, ATK Elkton
9:00 Pulse, Acquire, Control: Ten Years of On-Line High Resolution NMR in Refining, Petrochemical, and Food Manufacturing, P. J. Giammatteo and J. C. Edwards, Process NMR Associates
9:40 Process NIR at DuPont: A 20 Year Retrospective, C. H. Sohl, DuPont Engineering Research and Technology
10:20 Break
10:40 Rapid Composition Monitoring for Bio-Sustainable Processes: Useful Tools and Unmet Needs, A. M. Brearley, Consultant
11:20 PAT Applications for Pharmaceutical Processing, B. Diehl, Pfizer, Inc.

The NMR group of the Northern Jersey ACS section will be hosting a talk on Cryoprobe Technology combined with Principal Component Analysis.
The details of the talk are:

Wednesday, November 16, 2005 – The NJACS Proudly Presents:
“New Directions of CryoProbe Technology”
by Kimberly L. Colson, Ph.D. Bruker BioSpin Corp.

Abstract:
The utilization of new NMR technologies, such as CryoProbe technology, has revolutionized the applicability of NMR to many areas of study through a significant gain in sensitivity. In addition, advances in automation and the implementation of statistical approaches to examining variations amongst large datasets have enabled NMR to be used as a tool for classification of samples, and hence for examination of quality control, adulteration, quantification, biomarker discovery, etc.

CryoProbe technology enhances 1H, 13C, 15N, 19F, and 31P NMR sensitivity by a factor of four. This allows components in small quantities to be detected and allows NMR spectra to be acquired 16 times faster than previous methods. Although widely accepted for protein and small molecule structure analysis CryoProbe technology is not yet fully utilized in more challenging applications such as quality control, sample quantification, metabonomics and biomarker discovery. One reason is that the NMR data obtained on large datasets and on complex mixtures produces data that are often difficult to evaluate.

Simple comparison or quantification between large data sets is tedious and often impractical. However, combining the use of new CryoProbe Technology with the pattern recognition and multivariate statistical methods, like principle component analysis (PCA), allows rapid comparison of these large complex data sets. Principle component analysis algorithms can classify an object based on identification of inherent patterns in a set of experimental measurements or descriptors and facilitates the visualization of inherent patterns. Data set comparisons is therefore easier.

This powerful combination of CryoProbe technology, Statistical Analysis methods and new NMR experiments can be employed in many areas including the analysis of pharmaceuticals, natural products, metabolites, synthetic materials, foods, flavors, fragrances, and metabolites, to rapidly assess the composition of substances for quality control, mixing levels, product verification, and product identification. In this lecture we will explain the components that make up this new approach and demonstrate its utility with some examples.

Location: Woodbridge Hilton. Dinner at 6:30 p.m. Seminar at 7:00 p.m.

Buffet dinner: $10 for students and post-docs, $30 for all others, No charge for the seminary only. Beverages provided In the Bar at 5:45 p.m.

ASPeCT Magnet Technologies Ltd.

November 9th, 2005

A company that has recently been developing cutting edge permanent magnet systems is ASPeCT Magnet Technologies who are developing MRI and NMR magnets for industrial applications. The magnets are fully shielded permanent magnets of varying bore size that enable fully shimmed 60 MHz process FT-NMR systems as well as industrial and medical MRI. Our interest is obviously in their NMR magnets but there also possibilities developing to use gradient shimming to allow spatially specific high resolution spectra to be obtained from objects being imaged….eg. water/sugar NMR spectra obtained from citrus fruits. The ASPeCT website contains 2 presentations of the various technologies under development.

PNA - Who We Are

November 4th, 2005

Process NMR Associates LLC (PNA) was founded in 1997 by John Edwards and Paul Giammatteo in Danbury CT. Both were Ph.D. chemists working at the Texaco Fuels and Lubricants Research Center in Beacon, New York. Paul was group leader of process analytical and organic spectroscopy and John Edwards was the NMR spectroscopist for the Texaco corporation. Between them they have over 40 years of experience in NMR, organic spectroscopy, process analytical, and petroleum/petrochemical chemistry. Their laboratory includes a 300 MHz Varian NMR spectrometer for liquids analysis, a 200 MHz spectrometer for solids analysis, 2 benchtop TD-NMR spectrometers (2 MHz and 20 MHz), and three 60 MHz process NMR units.

Initially Process NMR Associates (PNA) concentrated on supporting the Invensys MRA product which had been formed by a JV between Invensys and the Elbit ATI NMR company. From 1997-2003 PNA was the application development and technical marketing consultants to that product. In 2003 PNA made a strategic decision to leave the relationship with Invensys and has concentrated on developing it’s analytical NMR service for industry. Currently PNA serves over 100 small and large companies for their liquid and solid-state NMR needs.

In October 2005 PNA entered into a JV arrangement with TTC Labs Inc (Fond du Lac WI). This JV is NMR Process Systems Inc and it will be involved in marketing, installing, servicing and enabling process NMR controlled APC and optimization projects.

Tailor-Made Hydrocarbons

November 4th, 2005

With the US public suddenly awakening to the fact that they have been squandering a finite natural resource with the current SUV craze, there is a huge amount of interest being generated in increase refining capacity, renewable sources of energy and the developoment of a crude oil substitute. With energy prices going to remain the same or increase, I think that Gasification Technology in combination with Fischer Tropsch synthesis will bail us out from the Mad Max scenario of 50 years hence.

Gasification can take many input feeds such as municipal waste, sewage, coal, plastics, bitumen, heavy oil, waste oils, biomass, etc. These are gasified to SynGas (H2/CO) which initially contains many impurities (metals, sulfur, oxides, chlorine etc) some impurities for a refractory (glass) that is removed from the gasifier and this refractory can be readily disposed as it encapsulates a lot of the “nasties”. The gaseous component of the product can be treated to yield pure syngas which can then be passed over Fischer Tropsch (FT) catalyst. The FT process is a gas-to-liquids process that recombines the elements present in the gas into hydrocarbons. The produced hydrocarbons can then be tailor made for the application (fuels, lubes, monomers) by cracking and/or hydroisomerization. FT is also a valuable technology as the large oil companies see it as a technology to develop their stranded gas deposits into a more readily transportable material so that these assets can be monetized.

From waste we will derive the energy required for the future. Shell, Exxon, British Petroleum, Syntroleum, and Sasol-Chevron are just a few of the companies working on GTL technology. Rentech Inc are another company working in collaboration with Texaco and Sasol (now Sasol-Chevron). Here is their statement regarding FT….GTLSite.pdf

13C NMR is the perfect way to monitor the detailed molecular chemistry of the products made by GTL processes. On-line 1H NMR or at line 13C would allow chemistry to be controlled on a timescale of minutes.

The information out there is vast from organizations such as Alaska Natural Gas Transportation and their ideas for the BP project at Nikiski. Modular designs of various process components will lead to small plants and improved product quality.

An excellent summary of the technology is found at Chemlink, Exxon, Sasol, DOE, Eltron Research, Foster Wheeler, SRI Consulting, Statoil, G-T-L, and Thailand.

GTL technology development will have fall out effects in the natural gas market – an excellent economics artive of LNG and GTL is found at EnergyPulse. A Congressional Report also investigates the GTL and natural gas markets. A great source of centralized energy news is EnergyBulletin.net which harvests many articles from around the world dealing with “peak oil” reporting. The Energy Blog is another excellent source of Energy Related Material.

The next big push will be to develop the oils shale, heavy oil and tar sand deposits that are found in Alberta, Utah, and the Orinoco Basin to name a few. These are the only deposits that can yield enough hydrocarbon for the GTL Technologies and meet energy needs for the foreseeable future. Strategically the development of these heavy resources to marketable fuels would remove the US dependence on imported oil.

Mid-Hudson ACS - New Website and Blog

November 4th, 2005

The Mid-Hudson Section of the American Chemical Society has a new website at http://www.midhudsonacs.org and a new blog at http://www.midhudsonacs.org/Blog

Mid Hudson ACS - November Meeting

November 4th, 2005

The Mid-Hudson Section of the American Chemical Society and the Chemistry Department of Vassar College Announce:
“Morphology Of Effect Materials” by Dr. Geoff Johnson, Engelhard Corporation, Wednesday, November 9, 2005 Time: 7:00 PM
Location: Vassar College , Mudd Chemistry Building, 3rd Floor – Science Visualization (Sci Vis) Lab
Contact Joseph Tanski (Vassar) at 845-437-7503 or by e-mail at jotanski@vassar.edu.

About the lecture: Classic pearlescent pigments have evolved far beyond the biologically derived mother-of-pearl that originally inspired them. The class of synthetics that includes pearlescent pigments is now called “effect materials.” This renaming emphasizes that appearance is the sum of many sensory effects, not just color. The most robust effect materials are composed of thin layers of metal oxides coated onto inorganic substrates. The layer structure determines color effects, but the morphology of the substrate plays a significant role in the overall effect. There is also a class of effect materials composed of bismuth oxychloride, in which the morphology of the BiOCl crystal is solely responsible for the observed effects.

About the speaker: Dr. Johnson is originally from South West England, near Bath . He received a BS in Chemistry from the University of Birmingham, UK and his MS in Chemistry from the École Nationale Supérieure de Chimie de Montpellier , France . He earned a PhD in Inorganic Materials Chemistry with Professor Mark Weller at the University of Southampton, UK. Dr. Johnson’s postdoctoral experience includes work in zeolite chemistry with Professor John Parise at SUNY Stony Brook and chemical catalysis at Worcester Polytechnic Institute with Fabio Ribeiro. He joined Engelhard in 2001 as a Research Chemist at the Corporate R&D facility in Iselin , New Jersey . In June 2004, he joined Engelhard’s Appearance and Performance Technology facility in Ossining , New York as a Senior Scientist. Dr. Johnson is a member of the Royal Society of Chemistry, American Chemical Society, Materials Research Society, and International Zeolite Association.

Directions to Vassar College : Vassar College is located at 124 Raymond Avenue in Poughkeepsie , NY . Refer to the following link for driving directions and campus map: www.vassar.edu/directions/. Enter the main entrance of the campus on Raymond Avenue .

Invensys divests interest in FoxboroNMR Ltd

November 4th, 2005

In June 2005 Invensys divested its majority stockholder position in FoxboroNMR Ltd the manufacturer of the NMR spectrometer upon which the Invensys MRA product is based. This means that FoxboroNMR will be marketing a process NMR solution through various market channels rather than having NMR systems sales occur exclusively through Invensys. Here is the press release concerning this item.

Polyolefins - Process TD-NMR

November 4th, 2005

Progression Inc (formerly Auburn and then Oxford Instruments) have been placing low field time-domain (TD) NMR spectrometers in the field for 15+ years. The main arena for their on-line analysis is polyolefins though they are now trying to extend their application base into coal and mining. They have 120+ systems in the field which is a lot considering that most NMR spectroscopists aren’t even aware of their existence. They have recently publised two application notes on TD-NMR applied to polypropylene resins and polyethylene resins. The bottom line is that most TD-NMR spectrometers can perform the analysis, however, the sample grabbing, pre-conditioning and delivery to the NMR are key.

It would be interesting to take detailed liquid-state 1H and 13C analyses, with complimentary solid-state 13C CP- and SP-MAS relaxation data in order to map the correlation between TD-NMR FID and CPMG profiles and the detailed chemistry of the samples.

NMR Console Purchase

November 4th, 2005

Today I bought a Varian Unity-400 console with three channels, solids amps, gradients, magnet leg assembly, HAL box and monitor panel for $2200. In the mid 90’s that spectrometer would have cost $300,000 +. NMR equipment seems to depreciate quicker than a Pontiac. My pack rat mentality is in full swing.

We operate a Varian VXR300S for liquids analysis and a Varian UnityPlus-200 for solids and liquids analysis. Sitting in the adjacent space of our of our office I have 2 full VXR-300 consoles as board swap for my liquids system, a VXR-400, a Varian 300 MHz R2D2 magnet, two 60 MHz process NMR spectrometers, and two boxes full of acquisition control board, ADC boards, sum-to-memory boards, etc.

I question why any small company would buy a new spectrometer when you must pay through the nose and watch it depreciate at a terrific rate. Then you have to deal with the fact that you are held hostage by the spectrometer manufacturer as failed components are only available through them initially at high exchange rates, and they will not ship you a board unless you have taken their maintenance course.

If you buy 10 year old spectrometers, either third party, or from ebay and other auctions, you can support yourself for pennies on the dollar. People actually laugh when I say I support the spectrometer service aspects of my business by surfing ebay and the internet.

One great third party supplier is Triangle Analytical who install and service spectrometers and take the worry of Cryogen refills away with their Helium (and Nitrogen if you want it) fill contracts. The perception of NMR as an expensive instrument to buy or maintain is simply not true any more.

If anyone has old NMR spectrometers, probes, magnets, or amplifiers laying around let me know…I can probably find a home for them.

 

For more information on this topic please contact:

John Edwards

Manager, Process and Analytical NMR Services

Process NMR Associates LLC,

87A Sand Pit Rd

Danbury, CT 06810, USA

Tel: (203) 744-5905   

 

 

 

 

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