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You are here: Home / The NMR Blog

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

May 4, 2012 by process nmr Chemistry, NMR, Process NMR

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 new magnet designs are 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.

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 – PD

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

March 21, 2012 by process nmr Chemistry, NMR

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

January 20, 2012 by process nmr Herbal Supplement, NMR, PAT Tagged: Acemannan, adulterant, adulteration, Aloe Vera, aloeverose, Dry Weight, glucomannan, glucose, maltodextrin, NMR, Raw material Analysis, testing, Whole Leaf Marker

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)

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

January 20, 2012 by process nmr NMR Tagged: IFPAC Conference, NMR, Talks

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/

New Conference Being Planned for Practical Applications of NMR in Industry

January 20, 2012 by process nmr NMR Tagged: CASSS, NMR Conference, on-line NMR, qNMR

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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