Quantitative NMR Analysis of Wine - qNMR
Here is an example of a 1H NMR analysis of a 2007 Red Wine submitted for chemical analysis by John W.
If you are interested in wine analysis please contact us.
Contact:
(203) 744-5905
This page contains NMR Method information posted on the PNA Blog Site
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 ManufacturingAn 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
Solid-State 13C NMR Analysis of Carbonaceous Materials
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.
Please inquire if you are interested in the details of the above analyses.
September 13, 2008
60 MHz TD-NMR System
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).
February 28, 2008
Process NMR Application: Spectro-Molecular Control for Enhanced Diesel Recovery
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.
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
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
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.
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.
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
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.
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
Naphtha Chemistry Analysis by 1H NMR
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
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.
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).
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
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
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
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
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
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.
NMR Applications in Food Quality
March 10th, 2006Quantification 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.
European Commision Report on Food Quality Sensors
March 1st, 2006A 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, 2006An 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, 2006Low 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, 2006Solid-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, 2006Practical Applications of NMR in Civil Engineering
February 26th, 2006NMR of Hydrocarbons - Online Papers Available
February 26th, 2006Though 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, 2006An 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, 2006An 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, 2006Where 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.
Trends in NMR Logging - Schlumberger Review Article
February 15th, 2006Oil 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, 2006Practical
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, 2006A 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)
NMR Spin Splittings and Chemical Shift Tutorials - NMR Chemical Shift Predictor
February 15th, 2006The 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.
Olive Oil Regional Authenticity from NMR Spectroscopy
February 8th, 2006High 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.
Spoilage of Wine observed by NMR of Intact Bottles
February 8th, 2006A 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, 2006Pattern 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, 2006Gérard 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, 200635 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.
IASC - NMR Methodology for Aloe Vera Certification
December 28th, 2005The 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.
Solid-State NMR and Polymorphism
December 1st, 2005At 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
For more information on this topic please contact:
Manager, Process and Analytical NMR Services
Process NMR Associates LLC,
87A Sand Pit Rd
Danbury, CT 06810, USA
Tel: (203) 744-5905