The Chemical Fingerprint of Beer from a Single Experiment with Minimum Sample Preparation – A Rapid Quantitive Analysis by 1H NMR Spectroscopy

NMR Spectroscopy is the premier tool utilized by chemists to obtain detailed chemical information on molecular structure and is used extensively in molecular structure verification, chemical purity analysis, and complex mixture analysis. We have developed a quantitative NMR analysis that yields a chemical fingerprint that brewers can utilize to follow detailed variations in the chemistry observed in the various stages of the brewing process (malting, mashing, boiling, fermentation, ageing, and blending). The analysis observes all molecules in the beer at the same time and each molecular component (acids, alcohols, amino acids, malt-oligosaccharides) yields a unique spectral fingerprint pattern that is related to the structure of the molecule. Though the spectrum consists of a large number of overlapped individual fingerprints it is possible to identify and quantify individual components because many components have signals that appear at unique and specific points in the spectrum. The quantitative analysis is performed by comparing the area under the individual molecule signals to that of an internal standard (Maleic Acid 99%). Molecular components are quantified on a weight/volume basis in mg/L (parts-per million). Ethanol is also quantified on a %volume/volume basis. The technique is not only applicable to the brewing process but is also being…

Read More

Quantitative 1H NMR Analysis of “Off-the-Shelf” Commercial Kombucha Beverages for Ethanol, Organic Acids and Residual Sugars Analysis

Over the past few years our analytical NMR service has been developing a detailed chemical fingerprint analysis of alcoholic beverages by quantitative 1H NMR (qHNMR). Beyond the typical analyses of beer, wine, port, hard cider, sake and spirits, we have been looking at other fermented beverages such as kombucha, kefir, kvass, mead, ginger beer and perry. As well as the final fermented beverages we have been actively investigating the various starting materials such as malt wort, apple juice, honey, grape juice, fruit juices, and tea. The NMR analysis can provide a rapid quantitative analysis without any sample preparation based on the molar ratio of integration value of unique molecular fingerprint peaks with the integrated signal of an internal standard. In our case we typically use maleic acid as an internal standard as it’s singlet signal peak appears in a non-overlapping are of the spectrum to the chemistry we are interested in following. The information that can be derived from the NMR experiment covers a wide dynamic range of component molecule concentrations from 10-100,000 ppm. The analysis observes all fully dissolved chemical constituents and the spectral response is linear with regard to all chemical types. As a primary analytical method the…

Read More

1H qNMR of Alcoholic Cider – Analysis of Small Molecule and Residual Sugar Chemistry

1H quantitative NMR (qNMR) has been utilized to assess the the small molecule and carbohydrate chemistry of a number of home-brewed and commercial alcoholic ciders. A quantitative chemistry distribution of the products of the various fermentations that occur in cider making. Malolactic fermentation as well as fermentation by saccharomyces and wild yeasts occur in the cider making process which traditionally occurred without the intentional addition of yeast by the manufacturer. The distribution of small molecules produced by the yeast and bacterial metabolomes at work in the process can yield information of the sensory perception of ciders produced in different ways. An investigation of the residual sugar chemistry of commercial ciders gives some indication of the process of sweetening commercial cider products with sugar additions after fermentation is complete. These typical commercial ciders are very different in chemistry distribution compared to very dry cider styles such as those found in the Basque region of Spain where fermentation is taken to the extreme resulting in complete conversion of sugars to alcohol but also glycerols to 1,3 propandiol. Finally it was decided to determine how much quantitative chemistry information could be obtained from benchtop NMR systems operating in the 60 MHz range. These…

Read More

Essential Oil Analysis – Comparison of 1H NMR from Benchtop and Supercon NMR Systems

1H NMR shows excellent promise to be utilized in the quality control and authentication of essential oils. In order to ascertain if benchtop NMR systems reveal adequate "1H spectral fingerprints" for this purpose we have run several hundred essential oils at 300 MHz (Varian Mercury-300 MVX by 1H, 13C, COSY, HETCOR, DEPT)  as well as at 82.3 MHz (Picospin 80), 60 MHz (Aspect-60), and 42.5 MHz (Magritek Spinsolve). The results plainly show that the spectrometers all yield similar proton line-widths with the difference in field strength leading to different levels of spectral dispersion and resolution. Though each spectrum is different it can plainly be seen that they all contain the same information with varying degrees of overlap. Chemometric and database comparative methods are being developed to allow identification of various essential oils as well as screening and quantifying different levels of adulteration. The figures below show examples from 6 different essential oils showing spectra obtained from all 4 spectrometers and plotted in the normalized chemical shift scale (ppm) as well as the absolute frequency scale (Hz).

Read More

Residual Catalytic Cracker – Heavy Petroleum Feedstream Properties from 1H NMR at 43 MHz

Back in October we presented a talk at Gulf Coast Conference that concerned the prediction of the chemical and physical properties of heavy petroleum feeds being converted to higher value product in a residual catalytic cracker (RCC). Over the years we have analyzed these materials by 300 and 60 MHz NMR and obtained good PLS-regression models that can adequately predict properties for real-time process control and optimization in a petroleum refinery. With the advent of a large number of new benchtop NMR systems we have been convincing ourselves that these types of analyses can be performed by systems such as the Magritek Spinsolve 43 MHz. We ran a series of samples that had been sitting around our lab for 15 years by dissolving them at about 50 volume% in a 50/50 CDCl3/CS2 solvent system. For each sample we had laboratory test data for a number of chemical and physical properties of interest to process engineers. We regressed the lab data variability against the variability in the Magritek 43MHz 1H NMR spectra and obtained cross-validated PLS models. The presentation material is given here at this link - Gulf Conference Presentation - 43 MHz RCC Feedstream Regression Models

Read More

Benchtop NMR – Screening Tool for Adulterated Herbal Supplements

Survey of Low Field NMR Spectrometer Platforms for Successful Screening of Sexual Enhancement and Weight Loss Supplements for Adulteration with Drugs and Drug Analogs John C Edwards1, Kristie M Adams2, and Anton Bzhelyansky2 1Process NMR Associates, Danbury, CT 2United States Pharmacopeial Convention, Rockville, MD The adulteration of dietary supplements (or natural health products) with synthetic pharmaceuticals is an area of increasing concern, which presents substantial risk to public health. Widely available in retail and via the Internet, these products are often marketed as sexual enhancement, weight loss and/or bodybuilding supplements. Unlike prescription drugs, supplements do not require premarket approval by FDA before they are made available for public consumption. In fact, the agency can only take investigational action after the adulterated product has caused harm and the adverse event has been reported via MedWatch (FDA’s online portal for voluntary reporting of adverse events associated with drugs, medical devices and dietary supplements). Development of analytical tools for screening and identification of adulterated products in the marketplace represents a significant step forward in the fight against adulterated dietary supplements. Several organizations, including AOAC and USP, have undertaken initiatives to evaluate and recommend analytical methodologies for screening supplements for adulteration. HPLC and mass…

Read More

From Atoms to Flavour: The Chemistry of Beer

Adam DiCaprio (ex PNA) gave an excellent Science Cafe Talk under the auspices of the ACS North Carolina Section at the Busy Bee Cafe in downtown Raleigh on December 2, 2014. CHanging gears from his previous talks he centered the discussion on malt and hop chemistry as well as an start-to-finish NMR analysis of production runs of a bottled commercial tavern ale. If you are interested in having Adam give a detailed chemistry seminar on beer at your section meetings please contact him directly at adam@process-nmr.com. A PDF version of his talk is available here .... ACS Science Cafe Talk - Dicaprio - Busy Bee Cafe - Raleigh NC - 12-2-14

Read More

Comparison of 1H NMR Spectra Obtained at 42, 60, 82, and 300 MHz – Fish Oil Omega-3 Ethyl Ester Supplement Example

Process NMR Associates is currently developing NMR applications based on direct measurement of chemometric modeling on NMR data obtained on numerous NMR platforms. Our intention is to develop solutions that can be executed on any NMR platform. With this in mind we are currently developing a fish oil analysis application that can provide the EPA and DHA omega-3 fatty acid content of fish oil supplements manufactured by an ethyl ester esterification process. We have obtained data at 42 MHz, 60 MHz, 82 MHz and 300 MHz. The chemometric modelling yielded PLS models for all 4 field strengths that yield effectively the same result - DHA can be measured to +/- ~1.1 wt% and EPA can be measured to +/- ~2.2 wt% by a 40 second 1H NMR measurement. THe correlation is derived from a  regression of the 1H NMR variability with primary GC analysis values. This analysis has been shown for the 300 and 60 MHz data in a previous post on this blog. The same analysis was also obtained, with similar results, on 42 and 82 MHz platforms proving that individual applications can be automated and provided at all relevant frequencies of NMR analysis whether on superconducting lab systems or permanent…

Read More

Presentations at SMASH 2014

"Beer Manufacturing and Analysis by NMR", John C. Edwards and Adam Dicaprio, Presented at the Mestrelab MNova Users, Meeting - SMASH, Atlanta, GA, September 7, 2014 Get PDF Here “Survey of Low Field NMR Spectrometer Platforms for Successful Screening of Sexual Enhancement and Weight Loss Supplements for Adulteration with Drugs and Drug Analogs", John C. Edwards, Kristie Adams, Anton Bzhelyansky , Presented at SMASH Conference, Atlanta, GA, September 7-10, 2014. Get PDF Here

Read More

Presentation and Posters – Magnetic Resonance in Food Conference 2014 – Cesena Italy

“Liquid and Solid-State 27Al qNMR of an Elemin Senonian Trace Minerals Supplement for Identification, Chemical Structure, Quantitation of Active Ingredient in the Product, and Product Stability”, Boris Nemzer, John C. Edwards, presented at XII International Conference on the Applications of Magnetic Resonance in Food Science: Defining Food by Magnetic Resonance, Cesena, Italy, May 20-23, 2014. Get PDF Here “Liquid and Solid-State Multinuclear 13C and 11B qNMR FruitexB Fructoborate Complex Nutritional Supplement. Identification, Chemical Structure, Quantitation of Active Ingredient in Product, and Product Stability”, Boris Nemzer, John C. Edwards, presented at XII International Conference on the Applications of Magnetic Resonance in Food Science: Defining Food by Magnetic Resonance, Cesena, Italy, May 20-23, 2014. Get PDF Here “1H qNMR of EPA and DHA Omega-3 Fatty Acid Esters - PLS Regression Models Obtained by 60 and 300 MHz NMR - At-Line and On-Line Monitoring of a Fish Oil Nutritional Supplement Manufacturing Process”, John C. Edwards, Paul J. Giammatteo, invited oral presentation at XII International Conference on the Applications of Magnetic Resonance in Food Science: Defining Food by Magnetic Resonance, Cesena, Italy, May 20-23, 2014. “Application of High Field and Cryogen-Free Bench-Top NMR Platforms to the Monitoring and Quantitation of PDE5 Inhibitor Adulteration of…

Read More

Herbal Supplement for Erectile Dysfunction Found to Contain Thio Structural Analog of Sildenafil (Viagra)

A herbal supplement marketed to alleviate erectile dysfunction was recently submitted for testing in our laboratory because it was surprisingly effective considering it should only contain the traditional herbals utilized for this problem such as Oyster, 2-Deoxy-D Glucose, Barberry, Snow Lotus, Bombyx Mori L., Ginger Root, Salfron Crocus. Above: 1H NMR of ED Herbal Supplement - this is an extract of the powder from  the capsules into 80:20 CD3CN:D2O - Observed suspicious specific small molecule peaks - herbals are usually broad featureless complex mixture spectra. This is something in different - a specific drug material appears to have been added.Comparison with the spectrum of Viagra (Sildenafil Citrate) below shows a strong similarity between the 2 active ingredients. We also obtained the COSY, 13C and DEPT NMR Spectra on the ED herbal supplement. These are shown below. The analysis of the NMR data led us to find that the extractable components of the sample contained predominantly Sulfoaildenafil (thioaildenafil) which is a strutural analog of Sildenafil (Viagra) and is not approved by any health regulation agency for use in erectile dysfunction medicines or supplements. Apparently these structural analogs to Viagra are found widely in herbal supplements sold for this malady. I guess…

Read More

Special Issue on Benchtop NMR systems in Wiley Journal “Magnetic Resonance in Chemistry” – please consider submitting a technical or review paper

I was just asked by Roberto Gil (Carnegie Mellon) to pull together a special issue if Magnetic Resonance in Chemistry" on the topic of Benchtop NMR. I will personally be hitting up everyone I know who is working in this area to provide technical papers on their work in this area. I also wanted to extend an invitation to the members of this group to submit a paper for this special issue. All topics will be considered but I would like to stay away from "traditional" 1H TD-NMR and restrict 1H TD-NMR applications to new approaches. On the high resolution side (45, 60, 80 MHz) I am hoping that applications with some real meat might be submitted rather than brochure type papers with just spectra of solvents and small molecules. Please feel free to contact me directly if you have ideas on submissions. My contact information is listed below. Sincerely, -- John C. Edwards, Ph.D. Manager, Process and Analytical NMR Services Process NMR Associates, LLC 87A Sand Pit Rd, Danbury, CT 06810, USA Tel: +1 (203) 744-5905 Cell: +1 (203) 241-0143 Skype: jcepna e-mail: john@process-nmr.com

Read More

Register to Attend PANIC 2014 ! Deadline for Poster Submissions is December 20

The 2nd Annual Practical Applications of NMR in Industry Conference (PANIC) will be held February 3-5 in Charlotte, NC. An excellent scientific agenda has been put together (see here). The Brochure is available here. Take note of the early registration (January 10, 2014) and poster submission (December 20, 2013) deadlines. John Edwards of Process NMR Associates is on the organizing committee of PANIC and has been appointed as Treasurer of the Conference company. John will be presenting an oral presentation in the one of the Nutraceutical Session:                NMR-Based Authentication of Nutraceuticals, Herbal Supplements, and Food Additives: Economic- and Efficacy-Driven Adulteration of Aloe Vera, Herbal Erectile Dysfunction Supplements, and Acacia Gum                                                                                                 John Edwards, Ph.D., Process NMR Associates, LLC - Biography Multinuclear NMR spectroscopy offers an outstanding ability to perform targeted and non-targeted analysis of nutraceuticals, herbal supplements, and food additives. Economic adulteration of these materials with lower…

Read More

MestreLab MNova Users Meeting – SMASH 2013 – PNA NMR Presentation

"Utilization of MNova in a Commercial NMR Testing Laboratory for: 1) Development of Automated Quantitative Analysis Methods by Direct Internal Standard NMR Measurements, and 2) Pre-Processing of Large NMR Datasets for Chemometric Regression Analyses to Derive Chemical and Physical Properties" - presented by John Edwards at the MNova Users Meeting - SMASH 2013 - Santiago de Compostela, Spain, September 22, 2013 PDF of Presentation Automated 1H qNMR analysis of complex mixtures - example of aloe vera powder 200x Final automated analysis output for aloe vera analysis - assignments and quantitative output. Chemometric analysis - spectrum processing and X-matrix preparation performed in MNova - ascii output imported into Eigenvector Research Solo for PLS regression or PCA analysis. Correlation of 1H NMR at 300 or 60 MHz with GC analysis of EPA and DHA content (wt%).  

Read More

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…

Read More

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…

Read More

ASTM F2259-03 (2008) – Determining the Chemical Composition of Alginates by 1H NMR Spectroscopy

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 lkength 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 methodology set forth in the test method.

Read More

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…

Read More

The RefinIR – FTIR-ATR Petroleum Product Analyzer

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

Read More

The Wood-Based Biorefinery in a Petroleum Depleted World

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…

Read More

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:

Read More

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…

Read More

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.  

Read More

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.

Read More

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.

Read More

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

Read More

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

Read More

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…

Read More

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.              

Read More

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

Read More

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…

Read More

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.

Read More

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…

Read More

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

Read More