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…

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References to 1H qNMR Applied to Fruit Juices and Alcoholic Beverages

qNMR “Validation of quantitative NMR”, F Malz, H Jancke, J Pharm Biomed Anal,  38, 813–823, (2005) “Quantitative 1H NMR spectroscopy”, S K Bharti, R Roy, Trends in Anal Chem, 35, 5-26 (2012) “NMR-based plant metabolomics: where do we stand, where do we go?”  H-K Kim, Y-H Choi, R Verpoorte Trends Biotech, 29(6), 267 (2011). “Universal quantitative NMR analysis of complex natural samples”, C Simmler, J G Napolitano, J B McAlpine, S-N Chen and G F Pauli, Current Opinion Biotech, 25, 51–59 (2014) “Quantitative 1H NMR: Development and Potential of a Method for Natural Products Analysis” G F Pauli, B U Jaki, D C Lankin, J. Nat. Prod., 68, 133-149 (2005) Juices “High-Field Proton NMR Studies of Apple Juices”, P S Belton, I Delgadillo, A M Gil, P Roma, F Casuscelli, I J Colquhoun, M J Dennis M Spraul, Mag Res Chem, 35, S52-S60 (1997) “Quantitative determination of (-)-epicatechin in cider apple juices by 1H NMR”, I Berregi , J I Santos , G del Campo , J I Miranda, Talanta 61 (2003) 139-145 “Use of the 1H Nuclear Magnetic Resonance Spectra Signals from Polyphenols and Acids for Chemometric Characterization of Cider Apple Juices”, G del Campo, J. I Santos, N…

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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…

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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…

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PNA to Present 4 Topics at the 2015 ACS North East Regional Meeting

John Edwards of Process NMR Associates will be presenting 4 papers at the 2015 ACS Northeast Regional Meeting that will be held in Ithaca, NY, June 10-13, 2015. ABSTRACT ID: 2283171 ABSTRACT TITLE: 1H qNMR of Alcoholic Cider - Analysis of Small Molecule and Residual Sugar Chemistry (final paper number: 43) SESSION: Food Chemistry SESSION TIME: 5:00 PM - 9:00 PM PRESENTATION FORMAT: Poster DAY & TIME OF PRESENTATION: Wednesday, June, 10, 2015, 5:00 PM - 9:00 PM ROOM & LOCATION: Emerson Suites - Campus Center ABSTRACT ID: 2283063 ABSTRACT TITLE: Nutritional Supplement and Diesel Fuel Application Development for Benchtop NMR Systems Operating at 42, 60, and 80 MHz – Equivalency with Supercon NMR (final paper number: 336) SESSION: Analytical Chemistry SESSION TIME: 9:00 AM - 11:30 AM PRESENTATION FORMAT: Oral DAY & TIME OF PRESENTATION: Friday, June, 12, 2015 from 9:45 AM - 10:05 AM ROOM & LOCATION: 222 - Williams Hall ABSTRACT ID: 2283105 ABSTRACT TITLE: Survey of Low Field NMR Spectrometer Platforms for Successful Screening of Sexual Enhancement and Weight Loss Supplements for Adulteration with Drugs and Drug Analogs (final paper number: 386) SESSION: Medicinal Chemistry SESSION TIME: 1:00 PM - 3:20 PM PRESENTATION FORMAT: Oral DAY…

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Beer and Cider Analysis – Example of Spectral Repeatability of Benchtop 60 MHz NMR System

Here is an example of spectral reproducibility. We are doing a lot of beer NMR at the moment on our 300 MHz NMR and for "giggles" we are running many samples through the various bench-top systems in our lab. We have been quantifying small organic acids (lactic, acetic, succinic , malic, citric, etc.) as they can give some idea of yeast activities and health during fermentation. We are also quantifying  and studying the 1,4/1,6 linkage distribution of residual dextrins. The series of superimposed spectra below consists of 28 spectra of a freeze dried beer sample (a unique Belgian Dubbel. Each spectrum was 128 pulses and took approximately 30 minutes per spectrum. So the superimposed data represents a 14 hour continuous stability test.The data was automatically processed with 16K zero-fill and autophase.It looks pretty damn good.   We've been looking at a lot of sour beers - here is a home-brewed Flemish Red aged in an oak barrel - note the high lactic and acetic content. We've also been analyzing a lot of hard ciders - commercial and home-brewed varitieties of various styles - very different from one sample to another in the small molecule and sugar chemistry.     1H…

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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

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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

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Presentation and Posters at PANIC 2014

“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 C. Edwards, invited presentation at the 2nd PANIC, Charlotte, NC, February 3-5, 2014. Get PDF Here “Development of an Automated Complex Mixture Analysis qNMR Method within Mestrelab MNova - Application to Aloe Vera and the Beer Brewing Process", John C. Edwards, Adam J. Dicaprio, Michael A. Bernstein, presented at the 2nd PANIC, Charlotte, NC, February 3-5, 2014. Get PDF Here “Small Molecule Chemistry of Spontaneously Fermented Coolship Ales”, Adam J. Dicaprio, John C. Edwards, presented at the 2nd PANIC, Charlotte, NC, February 3-5, 2014. Get PDF Here “Liquid and Solid-State 1H, 13C, and 11B qNMR Analysis of Fruitex-B®– A Calcium Fructoborate Comple: Chemical Structure and identification, quantitative analysis and stability study”, Boris Nemzer, John C. Edwards, presented at the 2nd PANIC, Charlotte, NC, February 3-5, 2014. Get PDF Here

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