Nikolai Kuhnert

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Organization: Jacobs University Bremen
Department: School of Engineering and Science, Chemistry
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Co-reporter:Roy N. D'Souza, Sergio Grimbs, Britta Behrends, Herwig Bernaert, Matthias S. Ullrich, Nikolai Kuhnert
Food Research International 2017 Volume 99, Part 1(Volume 99, Part 1) pp:
Publication Date(Web):1 September 2017
DOI:10.1016/j.foodres.2017.06.007
•Principal component analysis can distinguish between cocoa origins.•Several phenolic biomarkers to distinguish between fermented and unfermented cocoa•Larger A-type proanthocyanidins degrade rapidly upon fermentation.•Proanthocyanidin glycosides detected in phenolic extracts of cocoa.A comprehensive analysis of cocoa polyphenols from unfermented and fermented cocoa beans from a wide range of geographic origins was carried out to catalogue systematic differences based on their origin as well as fermentation status. This study identifies previously unknown compounds with the goal to ascertain, which of these are responsible for the largest differences between bean types. UHPLC coupled with ultra-high resolution time-of-flight mass spectrometry was employed to identify and relatively quantify various oligomeric proanthocyanidins and their glycosides amongst several other unreported compounds. A series of biomarkers allowing a clear distinction between unfermented and fermented cocoa beans and for beans of different origins were identified. The large sample set employed allowed comparison of statistically significant variations of key cocoa constituents.Download high-res image (161KB)Download full-size image
Co-reporter:Abhinandan Shrestha, Inamullah Hakeem Said, Anne Grimbs, Naika Thielen, Lucas Lansing, Hartwig Schepker, Nikolai Kuhnert
Phytochemistry 2017 Volume 144(Volume 144) pp:
Publication Date(Web):1 December 2017
DOI:10.1016/j.phytochem.2017.09.018
•The use of LC-MS to analyze hydroxycinnamates in Rhododendron leaves.•The identification of phytochemical markers for some Rhododendron species.•PCA and PLS-DA were performed on Rhododendron samples to study their differences.Hydroxycinnamates including free hydroxycinnamic acids and their chlorogenic acid derivatives and glycosides have been profiled in leaf extracts of 98 Rhododendron species using LC-MS techniques. In total, 69 hydroxycinnamic acid derivatives were identified in the leaves of 98 Rhododendron species. Some derivatives serve as unique phytochemical marker for a single species, whereas other compounds are limited to certain subgenera. The distribution of compounds among six different subgenera of Rhododendron was studied using PCA and PLS-DA. This contribution presents data that provide unique metabolomic insight in the distribution of a class of secondary metabolites within a large selection of species from the botanically diverse plant genus Rhododendron.Sixty-nine hydroxycinnamates were identified in the leaves of ninety-eight Rhododendron species. Some derivatives serve as a unique phytochemical marker for a single species.Download high-res image (86KB)Download full-size image
Co-reporter:Maria A. Patras, Rakesh Jaiswal, Nikolai Kuhnert
Food Chemistry 2017 Volume 237(Volume 237) pp:
Publication Date(Web):15 December 2017
DOI:10.1016/j.foodchem.2017.05.150
•Caffeoyl glucoses were profiled in tomato, pepper, chilli and aubergine.•Caffeoyl glucose regio- and stereochemical assignment was carried out.•A LC–MS method for caffeoyl glucose quantification was developed and validated.•Quantitative data for caffeoyl glucose isomers are reported.•The profiled extracts showed a larger isomer complexity than previously reported.Based on the recently developed tandem MS based hierarchical scheme for the identification of regioisomeric caffeoyl glucoses, selected vegetables were profiled with respect to their caffeoyl glucose content. The dietary plants profiled were tomato, pepper, chilli and aubergine, all members of the Solanaceae family. 6-O-caffeoyl glucose was found to be the predominant isomer. In processed food such as tomato puree and ketchup a larger number of caffeoyl-glucose isomers formed through acyl migration reactions were observed. A LC–MS based quantitative method was developed, validated and caffeoyl glucose regioisomers quantified for the first time in dietary plants with quantitative data obtained from representative 30 food samples.
Co-reporter:Sagar Deshpande, Marius Febi Matei, Rakesh Jaiswal, Bassem S. Bassil, Ulrich Kortz, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2016 Volume 64(Issue 38) pp:7298-7306
Publication Date(Web):August 11, 2016
DOI:10.1021/acs.jafc.6b02472
(−)-Quinic acid possess eight possible stereoisomers, which occur both naturally and as products of thermal food processing. In this contribution, we have selectively synthesized four isomers, namely, epi-quinic acid, muco-quinic acid, cis-quinic acid, and scyllo-quinic acid, to develop a tandem LC-MS method identifying all stereoisomeric quinic acids. Four derivatives have been unambiguously characterized by single-crystal X-ray crystallography. The missing diastereomers of quinic acid were obtained by nonselective isomerization of (−)-quinic acid using acetic acid/concentrated H2SO4 allowing chromatographic separation and assignment of all diastereomers of quinic acid. We report for the first time that a full set of stereoisomers are reliably distinguishable on the basis of their tandem mass spectrometric fragment spectra as well as their elution order. A rationale for characteristic fragmentation mechanisms is proposed. In this study, we also observed that muco-quinic acid, scyllo-quinic acid, and epi-quinic acid are present in hydrolyzed Guatemalan roasted coffee sample as possible products of roasting.Keywords: cis-quinic acid; coffee; epi-quinic acid; muco-quinic acid; scyllo-quinic acid;
Co-reporter:Mohamed Gamaleldin Elsadig Karar, Marius-Febi Matei, Rakesh Jaiswal, Susanne Illenberger and Nikolai Kuhnert  
Food & Function 2016 vol. 7(Issue 4) pp:2052-2059
Publication Date(Web):15 Mar 2016
DOI:10.1039/C5FO01412C
Plants rich in chlorogenic acids (CGAs), caffeic acids and their derivatives have been found to exert antiviral effects against influenza virus neuroaminidase. In this study several dietary naturally occurring chlorogenic acids, phenolic acids and derivatives were screened for their inhibitory activity against neuroaminidases (NAs) from C. perfringens, H5N1 and recombinant H5N1 (N-His)-Tag using a fluorometric assay. There was no significant difference in inhibition between the different NA enzymes. The enzyme inhibition results indicated that chlorogenic acids and selected derivatives, exhibited high activities against NAs. It seems that the catechol group from caffeic acid was important for the activity. Dietary CGA therefore show promise as potential antiviral agents. However, caffeoyl quinic acids show low bioavailibility and are intensly metabolized by the gut micro flora, only low nM concentrations are observed in plasma and urine, therefore a systemic antiviral effect of these compounds is unlikely. Nevertheless, gut floral metabolites with a catechol moiety or structurally related dietary phenolics with a catechol moiety might serve as interesting compounds for future investigations.
Co-reporter:Hande Karaköse, Rakesh Jaiswal, Sagar Deshpande, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2015 Volume 63(Issue 13) pp:3338-3347
Publication Date(Web):February 20, 2015
DOI:10.1021/acs.jafc.5b00838
Mono- and diacyl chlorogenic acids undergo photochemical trans–cis isomerization under ultraviolet (UV) irradiation. The photochemical equilibrium composition was established for eight selected derivatives. In contrast to all other dicaffeoylquinic acid derivatives, cynarin (1,3-dicaffeoylquinic acid) undergoes a [2 + 2] photochemical cycloaddition reaction, constituting a first example of Schmidt’s law in a natural product family. The relevance of photochemical isomerization in agricultural practice was investigated using 120 samples of Stevia rebaudiana leave samples grown under defined cultivation conditions. Ratios of cis to trans chlorogenic acids were determined in leaf samples and correlated with climatic and harvesting conditions. The data indicate a clear correlation between the formation of cis-caffeoyl derivatives and sunshine hours prior to harvesting and illustrate the relevance of UV exposure to plant material affecting its phytochemical composition.
Co-reporter:Hande Karaköse, Anja Müller, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2015 Volume 63(Issue 41) pp:9188-9198
Publication Date(Web):September 3, 2015
DOI:10.1021/acs.jafc.5b01944
Stevia rebaudiana (Bertoni) is a plant from the Asteraceae family with significant economic value because of the steviol glycoside sweeteners in its leaves. Chlorogenic acids and flavonoid glycosides of S. rebaudiana from seven different botanical varieties cultivated over two years and harvested three times a year in eight European locations were profiled and quantified in a total of 166 samples. Compounds quantified include chlorogenic acids as well as flavonoid glycosides and aglycons. All phenolic concentration profiles show a perfect Gaussian distribution. Principal component analyses allow distinction between varieties of different geographical origin and distinction between different plant varieties. Although concentrations of all chlorogenic acids showed a positive correlation, no correlation was observed for flavonoid glycosides. Conclusions from these findings with respect to the biosynthesis and functional role of phenolics in S. rebaudiana are discussed.
Co-reporter:Ghada H. Yassin, Jan H. Koek, Nikolai Kuhnert
Food Chemistry 2015 180() pp: 272-279
Publication Date(Web):
DOI:10.1016/j.foodchem.2015.01.108
Co-reporter:Rakesh Jaiswal and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2014 Volume 62(Issue 6) pp:1261-1271
Publication Date(Web):January 22, 2014
DOI:10.1021/jf4053989
Bottle gourd, Lagenaria siceraria Stand. (Cucurbitaceae), fruit is used in folk medicines and for culinary purposes in Asia. The phenolics of bottle gourd fruit were investigated qualitatively by LC–MSn. Twenty-two phenolic glycosides were detected and characterized on the basis of their unique fragmentation pattern in the negative ion mode tandem MS spectra. Twenty of them were extracted for the first time from this source, and twelve of them have not been reported previously in nature. It was also possible to distinguish between the individual classes of isobaric phenolic glycosides by tandem and high-resolution mass spectrometry. In this study we also discuss the mass spectrometric fragmentation mechanism of 6-(hydroxycinnamoyl)glucoses. This is the first report of the full characterization of phenolic glycosides of bottle gourd fruit by LC-MS2–4.
Co-reporter:Sagar Deshpande, Rakesh Jaiswal, Marius Febi Matei, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2014 Volume 62(Issue 37) pp:9160-9170
Publication Date(Web):August 12, 2014
DOI:10.1021/jf5017384
Acyl migration in chlorogenic acids describes the process of migration of cinnamoyl moieties from one quinic acid alcohol group to another, thus interconverting chlorogenic acid regioisomers. It therefore constitutes a special case of transesterification reaction. Acyl migration constitutes an important reaction pathway in both coffee roasting and brewing, altering the structure of chlorogenic acid initially present in the green coffee bean. In this contribution we describe detailed and comprehensive mechanistic studies comparing inter- and intramolecular acyl migration involving the seven most common chlorogenic acids in coffee. We employe aqueous acidic and basic conditions mimicking the brewing of coffee along with dry roasting conditions. We show that under aqueous basic conditions intramolecular acyl migration is fully reversible with basic hydrolysis competing with acyl migration. 3-Caffeoylquinic acid was shown to be most labile to basic hydrolysis. We additionally show that the acyl migration process is strongly pH dependent with increased transesterification taking place at basic pH. Under dry roasting conditions acyl migration competes with dehydration to form lactones. We argue that acyl migration precedes lactonization, with 3-caffeoylquinic acid lactone being the predominant product.
Co-reporter:Rakesh Jaiswal, Marius Febi Matei, Viktorija Glembockyte, Maria Alexandra Patras, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2014 Volume 62(Issue 38) pp:9252-9265
Publication Date(Web):September 3, 2014
DOI:10.1021/jf501210s
A chromatographic method was developed to separate all 10 regio- and stereoisomers of caffeoylglucose. Following chromatographic separation on reversed phase, the fragmentation behavior of all 10 regio- and stereoisomers of caffeoylglucose has been investigated using LC–MSn. It is possible to discriminate between each of the isomers based on their characteristic fragment spectra and order of elution, including those for which commercial standards are not available. On the basis of the synthesis of authentic standards for 6-caffeoylglucose and 3-caffeoylglucose and nonselective further synthesis of suitable mixtures of isomers, it was possible to fully assign regiochemistry of all 10 isomeric compounds and stereochemistry of eight isomeric compounds. Their fragmentation pattern was rationalized based on assuming different hydrogen-bonding arrays of gas-phase ions opening distinct fragmentation pathways. An analysis of yerba maté extract showed all 10 regio- and stereoisomers of caffeoylglucose to be present in this dietary material, which could all be assigned to regioisomeric level and eight to stereoisomeric level.
Co-reporter:Ghada H. Yassin, Jan H. Koek, Sujatha Jayaraman, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2014 Volume 62(Issue 40) pp:9848-9859
Publication Date(Web):September 12, 2014
DOI:10.1021/jf502220c
Thearubigins are the most abundant phenolic pigments found in black tea, produced by enzymatic oxidation of green tea flavan-3-ols in tea fermentation of until recently unknown composition. In this study electrospray ionization tandem LC-MSn experiments have been applied for the characterization of crude thearubigins isolated from black tea not exceeding 1000 Da. The aim of this study is to confirm the oxidative cascade hypothesis of tea fermentation. The data revealed the presence of two novel classes of compounds in thearubigin fractions. The first class of compounds revealed the presence of polyhydroxylated dimers of the theanaphthaquinone and theasinensin C structures, which were consistent with the polyhydroxylation hypothesis previously formulated. Furthermore, new classes of peroxo-/epoxy- compounds in the series of theasinensin A were identified, thus indicating the presence of H2O2 and its important contribution as a nucleophile in the tea fermentation process.
Co-reporter:Rakesh Jaiswal;Mohamed Gamaleldin Elsadig Karar;Haidar Abdel Gadir
Phytochemical Analysis 2014 Volume 25( Issue 6) pp:567-576
Publication Date(Web):
DOI:10.1002/pca.2530

ABSTRACT

Introduction

Ixora coccinea L. leaves and stem are used in traditional Sudanese and Ayurvedic medicinal systems for the treatment of diarrhoea, fever, headache, skin diseases, eye trouble, wounds, sores and ulcers. Recent studies show that I. coccinea has anti-oxidant, anti-bacterial, anti-cancer, anti-inflammatory, analgaesic, anti-diarrhoeal, hepatoprotective, cardioprotective, anti-mutagenic, wound healing and anti-tumour activities. Ixora coccinea is a rich source of polyphenols such as proanthocyanidins, flavonoids, flavonoids glycosides and tannins.

Objectives

To develop a LC–MSn method for the identification and characterisation of phenolic compounds of I. coccinea L. leaves and stem.

Methods

Aqueous methanolic (70% methanol) extracts of I. coccinea leaves and stem were used for LC–MSn to ensure efficient extraction of phenolics. A C18 amide reverse-phase HPLC column allowed separation of the phenolic compounds, including different isomers. For the LC–MS measurements, negative ion mode was used in order to obtain better tandem mass spectra and high-resolution mass spectra.

Results

The phenolics were identified by their typical UV absorptions at 254, 280 and 320 nm. All the flavonol glycosides showed a neutral loss of the glycan part; hydroxycinnamates showed loss of the cinnamoyl/cinnamic acid part; while proanthocyanidins showed a Diels-Alder fragment in negative ion mode mass spectra.

Conclusion

It was possible to identify C-3 and C-7 flavonol glycosides by their order of elution and it was also possible to predict the glycosylation position in flavonol diglycosides from their tandem mass spectra. Copyright © 2014 John Wiley & Sons, Ltd.

Co-reporter:Sagar Deshpande, Rasha M. El-Abassy, Rakesh Jaiswal, Pinkie Eravuchira, Bernd von der Kammer, Arnulf Materny and Nikolai Kuhnert  
Analytical Methods 2014 vol. 6(Issue 10) pp:3268-3276
Publication Date(Web):07 Feb 2014
DOI:10.1039/C3AY41970C
In this contribution we have analysed aqueous methanolic extracts of a total of 38 green bean coffee samples, which vary in terms of the coffee variety and processing conditions. We have characterised these extracts using NMR-, IR- and CD-spectroscopies along with LC-MS. All spectroscopic data have been analysed by principal component analysis (PCA) using different PCA processing parameters by an unsupervised non-targeted approach. We could show that the distinction between different groups of samples, in particular, Arabica versus Robusta green coffee beans can be successfully analysed by IR-spectroscopy and LC-MS. Surprisingly both CD- and NMR-spectroscopies fail to achieve, in this case, an adequate level of distinction. This is, to the best of our knowledge, the first study that directly compares the value of various spectroscopic techniques if multivariant statistical techniques are employed to them.
Co-reporter:Rakesh Jaiswal, Elias A. Halabi, Mohamed Gamaleldin Elsadig Karar, Nikolai Kuhnert
Phytochemistry 2014 Volume 106() pp:141-155
Publication Date(Web):October 2014
DOI:10.1016/j.phytochem.2014.07.018
•The phenolics of Ilex glabra L. Gray (Aquifoliaceae) leaves were investigated qualitatively by LC–MSn.•Fifteen phenolics were detected for the first time in nature.•The regiochemistry was assigned based on the tandem mass spectra.The phenolics of the leaves of Ilex glabra L. Gray (Aquifoliaceae) were investigated qualitatively by LC–MSn. Thirty-two phenolics were detected and characterised on the basis of their unique fragmentation pattern in the negative ion mode tandem MS spectra. All of them were extracted for the first time from this source and fifteen of them were not reported previously in nature. For the positive identification of phenolic glucosides by LC–MSn a series of authentic standards and experiments were carried out. This is the first report of a full characterisation of 3,4-dihydroxybenzoyl glucosides, 3,4-dihydroxybenzyl glucosides, 4-hydroxybenzoyl glucosides, chlorogenic acid glucosides and vanillic acid glucosides by LC–MS2−4.Graphical abstractWe have developed an LC–MSn method for the identification and characterisation of 3,4-dihydroxybenzyl alcohol, 4-hydroxybenzyl alcohol and chlorogenic acid glucosides from Ilex glabra L. Gray leaves.
Co-reporter:Rakesh Jaiswal, Heiko Müller, Anja Müller, Mohamed Gamaleldin Elsadig Karar, Nikolai Kuhnert
Phytochemistry 2014 Volume 108() pp:252-263
Publication Date(Web):December 2014
DOI:10.1016/j.phytochem.2014.08.023
•The phenolics of Lonicera henryi L. (Caprifoliaceae) leaves were investigated qualitatively by LC–MSn.•Thirteen chlorogenic acid glycosides were detected for the first time in nature.•The regiochemistry of chlorogenic acid glycosides was assigned based on the tandem mass spectra.The chlorogenic acids, chlorogenic acid glycosides and flavonoids of the leaves of Lonicera henryi L. (Caprifoliaceae) were investigated qualitatively by liquid chromatography tandem mass spectrometry. Thirty-one chlorogenic acids and their glycosides were detected and characterized to their regioisomeric level on the basis of their unique fragmentation pattern in the negative ion mode tandem MS spectra. All of them were extracted for the first time from this source and thirteen of them were not reported previously in nature. For the positive identification of chlorogenic acid glycosides by LC–MSn, multiple reaction monitoring and targeted MSn experiments were performed. We have developed an LC–MSn method for the systematic identification of chlorogenic acid glycosides and were also able to discriminate between chlorogenic acids and their isobaric glycosides. It was also possible to discriminate between 5-O-(3′-O-caffeoyl glucosyl)quinic acid and 5-O-(4′-O-caffeoyl glucosyl)quinic acid by LC–MSn. This method can be applied for the rapid and positive identification of chlorogenic acids and their glycosides in plant materials, food and beverages.We have developed the LC–MSn and LC–HRMS methods for the identification and characterization of chlorogenic acid glycosides from Lonicera henryi L. (Caprifoliaceae) leaves.
Co-reporter:Rakesh Jaiswal, Hande Karaköse, Susanne Rühmann, Katharina Goldner, Michael Neumüller, Dieter Treutter, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2013 Volume 61(Issue 49) pp:12020-12031
Publication Date(Web):October 24, 2013
DOI:10.1021/jf402288j
Plums (Prunus domestica L. and Prunus salicina L.) are edible fruits mostly consumed in America, China, and Europe. We have used LC-MSn to detect and characterize the phenolic compounds in plum varieties. Forty-one phenolics were detected comprising caffeoylquinic acids, feruloylquinic acid, p-coumaroylquinic acids, methyl caffeoylquinates, methyl p-coumaroylquinate, caffeoylshikimic acids, catechin, epicatechin, rutin, esculin, quercetin, quercetin-3-O-hexosides, dimeric proanthocyanidins, trimeric proanthocyanidins, caffeoyl-glucoside, feruloyl-glucoside, p-coumaroyl-glucoside, vanillic acid-glucosides, 3,4-dihydroxybenzoyl-glucoside, quercetin-3-O-pentosides, quercetin-3-O-rhamnoside, quercetin-pentoside-rhamnosides, and 3-p-methoxycinnamoylquinic acid. This is the first time when 3-p-methoxycinnamoylquinic acid is reported in nature. Chlorogenic acids and proanthocyanidins were the major phenolics present in plums. Furthermore, HPLC with DAD and chemical reaction detection was used to generate quantitative phenolic fingerprints from the fruit flesh of 33 plum varieties. The predominant compound was 3-caffeoylquinic acid in nearly all varieties studied; generally, however, the qualitative and quantitative profiles showed high diversity even among closely related progenies.
Co-reporter:Agnieszka Golon, Francisco Javier González, Juan Z. Dávalos, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2013 Volume 61(Issue 3) pp:674-684
Publication Date(Web):December 20, 2012
DOI:10.1021/jf302135k
Many dietary products containing polysaccharides, mostly starch and cellulose, are processed by thermal treatment. Similarly to the formation of caramel from mono- and disaccharides, the chemical structure of the carbohydrates is dramatically altered by heat treatment. This contribution investigates the products of thermal decomposition of pure starch and cellulose as model systems followed by an investigation of bread obtained at comparable conditions using a combination of modern mass spectrometry techniques. From both starch and cellulose, dehydrated oligomers of glucose and dehydrated glucose have been predominately observed, with oligomers of more than four glucose moieties dominating. Moreover, disproportionation and oligomers with up to six carbohydrates units are formed through unselective glycosidic bond breakage. MALDI-MS data confirm the presence of the majority of products in toasted bread.
Co-reporter:Agnieszka Golon and Nikolai Kuhnert  
Food & Function 2013 vol. 4(Issue 7) pp:1040-1050
Publication Date(Web):12 Feb 2013
DOI:10.1039/C3FO30352G
The chemical analysis of caramel, formed upon heating of carbohydrates, remains a significant challenge due to the complexity of the resulting product mixture. Identification of the products formed upon heating of monosaccharides including fructose, mannose, galactose, arabinose and ribose is essential to understand the composition and properties of carbohydrate-rich processed foods. In this work, we report on the use of combined mass spectrometry techniques, including high performance liquid chromatography and electrospray ionization multi-stage tandem mass spectrometry (ESI-MSn). The composition of the obtained caramel was examined by high resolution mass spectrometry along with van Krevelen and Kendrick analysis. We found that caramel is composed of oligomers with up to six carbohydrate units formed through unselective glycosidic bond formation, their dehydrated products by losing up to eight water molecules, hydrated products and disproportionation products. An accurate mass measurement and subsequent fragment ion studies of all caramel samples (around 40 compounds) can thus be identified. Glycosidic bond and ring cleavages of sugar moieties were the major observable fragmentation pathways during this experiment. The innovative analytical strategies for the complex mixture analysis used provide a comprehensive account of the chemical composition of caramel, one of the most popular dietary materials over the world.
Co-reporter:Nikolai Kuhnert, Farnoosh Dairpoosh, Ghada Yassin, Agnieszka Golon and Rakesh Jaiswal  
Food & Function 2013 vol. 4(Issue 8) pp:1130-1147
Publication Date(Web):28 Feb 2013
DOI:10.1039/C3FO30385C
In this contribution we review our work on the characterisation of processed food. We review novel methods and analysis strategies developed to account for the composition of extraordinarily complex materials such as black tea thearubigins, coffee melanoidines and thermally treated carbohydrates. Our methods are mainly based on modern mass spectrometry and are introduced and critically discussed. A series of novel previously unpublished data interpretation strategies are presented as well. Finally an evaluation of the insight obtained in the composition of selected processed foods is given discussing potential consequences for assessing beneficial and adverse health effects of processed food.
Co-reporter:Hany F. Nour, Agnieszka Golon, Nikolai Kuhnert
Tetrahedron Letters 2013 Volume 54(Issue 32) pp:4139-4142
Publication Date(Web):7 August 2013
DOI:10.1016/j.tetlet.2013.05.085
A novel class of chiral enantiomerically pure C2-symmetric polyamide macrocycles has been synthesized from the reaction of chiral dioxolane dicarbohydrazides, obtained from commercially available tartaric acid, and aromatic diisocyanates. The novel macrocycles form in almost quantitative yields in a chemoselective [2+2]-cyclocondensation reaction under conformational bias of the dicarbohydrazides. The reaction takes place in anhydrous THF at a relatively high concentration of reactants without addition of external templates or application of high dilution conditions. The structures of the novel polyamide macrocycles were verified and fully assigned by 1H NMR, 13C NMR, 2D ROESY NMR, 2D HMBC, 2D HMQC, DEPT 135, FT IR, and CD spectroscopy.
Co-reporter: Dr. Nikolai Kuhnert
Chemie in unserer Zeit 2013 Volume 47( Issue 2) pp:80-91
Publication Date(Web):
DOI:10.1002/ciuz.201300589

Abstract

Alle Pflanzen stellen Polyphenole her, die sowohl strukturell als auch in ihren chemischen und biologischen Eigenschaften eine faszinierende Vielfalt zeigen. Während den pflanzlichen Organismen Polyphenole als UV-Lichtschutz, als chemische Verteidigung gegen Mikroorganismen und Pflanzenfresser dienen und durch ihre Färbung Insekten anlocken, nutzen Menschen ihre Eigenschaften in industriellen Prozessen, dabei vor allem zur Verbesserung unserer Gesundheit. Polyphenole sind sowohl als Bestandteil unserer täglichen Nahrung als auch als Bestandteil traditioneller Arzneipflanzen in der Lage, in vielfältiger Weise mit den biochemischen Strukturen des menschlichen Stoffwechsels zu interagieren und Symptome wie auch Ursachen vieler Erkrankungen zu beeinflussen. Die Wirkung der Polyphenole als Antioxidantien, die viele Jahre lang zur Erklärung der gesundheitsförderlichen Eigenschaften der Polyphenole herangezogen wurde, ist nach neuesten Erkenntnissen in den Hintergrund getreten. Neue Ansätze zur Erklärung der biologischen Eigenschaften der Polyphenole haben sich in den letzten Jahren entwickelt, die die chemischen Veränderungen der Polyphenole durch Lebensmittelprozessierung und Metabolismus berücksichtigen und sich nur auf Verbindungen konzentrieren, die gut bioverfügbar sind. Die Verstoffwechselung und die Wirkweise der Polyphenole im menschlichen Körper hat sich in den letzten Jahren als komplizierter erwiesen als lange angenommen. Eine klare Antwort auf die Frage, welche Verbindungen gesund sind und wie diese wirken, ist erneut Gegenstand aktueller Forschung geworden.

Polyphenolics are ubiquitous secondary plant metabolites. Polyphenolics serve in plants as UV protecting agents, flower pigments und protecting agents against microorganisms and herbivores. Humans have taken advantage of the chemical properties of phenolics for centuries in leather tanning, herbal remedies or food production. Most importantly all dietary plants contain ample amounts of polyphenolics able to protect them from multifactorial diseases such as cardiovascular disease, cancer or diabetis. Which compounds, however, are responsible for the beneficial health effect of a diet rich in plants and how do they function in the human body? This contribution summarises various aspects of polyphenol chemistry and biology with an emphasis on polyphenolics in the human diet.

Co-reporter:Dr. Nikolai Kuhnert
Angewandte Chemie 2013 Volume 125( Issue 42) pp:11148-11150
Publication Date(Web):
DOI:10.1002/ange.201304548
Co-reporter:Dr. Nikolai Kuhnert
Angewandte Chemie International Edition 2013 Volume 52( Issue 42) pp:10946-10948
Publication Date(Web):
DOI:10.1002/anie.201304548
Co-reporter:Hany F. Nour, Nadim Hourani and Nikolai Kuhnert  
Organic & Biomolecular Chemistry 2012 vol. 10(Issue 22) pp:4381-4389
Publication Date(Web):03 Apr 2012
DOI:10.1039/C2OB25171J
A total of twelve novel enantiomerically pure tetra-carbohydrazide cyclophane macrocycles have been synthesised in quantitative yields by reacting chiral (4R,5R)- and (4S,5S)-1,3-dioxolane-4,5-dicarbohydrazides with aromatic bis-aldehydes in a [2+2]-cyclocondensation reaction. The compounds show a dynamic behaviour in solution, which has been rationalized in terms of an unprecedented conformational interconversion between two conformers one stabilised by intramolecular hydrogen bonding and π–π stacking interactions.
Co-reporter:Rakesh Jaiswal, Michael H. Dickman and Nikolai Kuhnert  
Organic & Biomolecular Chemistry 2012 vol. 10(Issue 27) pp:5266-5277
Publication Date(Web):11 May 2012
DOI:10.1039/C2OB25124H
We report on a diastereoselective synthesis of six derivatives of caffeoyl- and feruloyl-muco-quinic acids. All the muco-quinic acid derivatives were obtained in excellent yield in five steps starting from quinic acid, caffeic acid and ferulic acid. Allyl ether protection of trans-hydroxy cinnamic acids was here introduced to chlorogenic acids synthesis. We show that muco-quinic acid derivatives, which are formally diastereoisomers of chlorogenic acids, can be readily distinguished by their tandem mass spectra
Co-reporter:Marius Febi Matei, Rakesh Jaiswal, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2012 Volume 60(Issue 49) pp:12105-12115
Publication Date(Web):October 30, 2012
DOI:10.1021/jf3028599
Coffee is one of the most popular and consumed beverages in the world and is associated with a series of benefits for human health. In this study we focus on the reactivity of chlorogenic acids, the most abundant secondary metabolites in coffee, during the coffee brewing process. We report on the hydroxylation of the chlorogenic acid cinnamoyl substituent by conjugate addition of water to form 3-hydroxydihydrocaffeic acid derivatives using a series of model compounds including monocaffeoyl and dicaffeoylquinic acids and quinic acid lactones. The regiochemistry of conjugate addition was established based on targeted tandem MS experiments. Following conjugate addition of water a reversible water elimination yielding cis-cinnamoyl derivatives accompanied by acyl migration products was observed in model systems. We also report the formation of all of these derivatives during the coffee brewing process.
Co-reporter:Agnieszka Golon and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2012 Volume 60(Issue 12) pp:3266-3274
Publication Date(Web):March 1, 2012
DOI:10.1021/jf204807z
Caramel is one of mankind’s best known dietary materials obtained from carbohydrates by heating. Much effort has been expended toward the chemical characterization of the components of caramel but impeded by a lack of suitable analytical techniques sufficiently powerful for providing insight into an extraordinarily complex material. This paper reports the characterization of caramel formed by heating from glucose, fructose, and saccharose using a conceptually novel combination of mass spectrometrical techniques. The analytical strategy employed uses high-resolution mass spectrometry (MS) followed by targeted liquid chromatography–tandem MS experiments. Caramel is composed from several thousand compounds formed by a small number of unselective and chemoselective reactions. Caramelization products include oligomers with up to six carbohydrate units formed through unselective glycosidic bond formation, dehydration products of oligomers losing up to a maximum of eight water molecules, hydration products of sugar oligomers, disproportionation products, and colored aromatic products.
Co-reporter:J. Warren Drynan, Michael N. Clifford, Jacek Obuchowicz, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2012 Volume 60(Issue 18) pp:4514-4525
Publication Date(Web):April 17, 2012
DOI:10.1021/jf205125y
Thearubigins are the quantitatively major phenolic compounds in black tea, accounting for some 60–70% of the solids in a typical black tea infusion. MALDI-TOF mass spectra for caffeine-precipitated SII thearubigins (SII CTRs) from 15 different commercial teas support previous conclusions that SII CTRs are polyhydroxylated oligomers (rather than polymers) of catechins and catechin gallates in redox equilibrium with their quinone counterparts. Some 4500 peaks were revealed in a mass range from m/z 500 to 2100. Polyphenols are redox-susceptible and readily generate artifacts during MALDI-TOF analysis when the matrix is also redox-susceptible. Of the nine matrices evaluated, 3′,4′,5′-trihydroxyacetophenone (F) provided the best compromise between signal intensity and redox artifact formation.
Co-reporter:Nadim Hourani and Nikolai Kuhnert  
Analytical Methods 2012 vol. 4(Issue 3) pp:730-735
Publication Date(Web):20 Feb 2012
DOI:10.1039/C2AY05249K
A novel direct-infusion atmospheric pressure chemical ionization mass spectrometry method to identify saturated straight-chain hydrocarbons in light shredder waste fraction has been developed. Ionization of alkanes under nitrogen gas source favored hydrogen abstraction producing mostly (M–H)+ ions, which strictly correspond to their respective series of n-alkanes between n-decane (C10) and n-tetra-contane (C40). The method is shown to produce intact gas phase ions of n-alkane in both reference and real life waste samples. APCI-MS2 fragmentation data assisted in the structural verification of the n-alkanes investigated in both standard and waste mixtures.
Co-reporter:Hany F. Nour, Marius F. Matei, Bassem S. Bassil, Ulrich Kortz and Nikolai Kuhnert  
Organic & Biomolecular Chemistry 2011 vol. 9(Issue 9) pp:3258-3271
Publication Date(Web):23 Mar 2011
DOI:10.1039/C0OB00944J
2-Functionalised aromatic monoaldehydes were synthesised in good to excellent yields by reacting 4-bromo-2-fluorobenzaldehyde with different secondary amines and phenol. The Suzuki-coupling reaction of the newly functionalised aromatic monoaldehydes with 4-formylphenylboronic acid afforded the corresponding 2-functionalised-4,4′-biphenyldialdehydes in good yields (47–85%). The [3+3]-cyclocondensation reactions of the 2-functionalised-4,4′-biphenyldialdehydes with (1R,2R)-1,2-diaminocyclohexane afforded a mixture of regioisomeric C3-symmetrical and non-symmetrical trianglimines. Reduction of the C3-symmetrical and the non-symmetrical trianglimines with NaBH4 in a mixture of THF and MeOH afforded the corresponding trianglamines in high yields.
Co-reporter:Rakesh Jaiswal and Nikolai Kuhnert  
Food & Function 2011 vol. 2(Issue 1) pp:63-71
Publication Date(Web):06 Dec 2010
DOI:10.1039/C0FO00125B
Burdock (Arcticum lappa L.) roots are used in folk medicine and also as a vegetable in Asian countries especially Japan, Korea, and Thailand. We have used LC-MSn (n = 2–4) to detect and characterize in burdock roots 15 quantitatively minor fumaric, succinic, and malic acid-containing chlorogenic acids, 11 of them not previously reported in nature. These comprise 3-succinoyl-4,5-dicaffeoyl or 1-succinoyl-3,4-dicaffeoylquinic acid, 1,5-dicaffeoyl-3-succinoylquinic acid, 1,5-dicaffeoyl-4-succinoylquinic acid, and 3,4-dicaffeoyl-5-succinoylquinic acid (Mr 616); 1,3-dicaffeoyl-5-fumaroylquinic acid and 1,5-dicaffeoyl-4-fumaroylquinic acid (Mr 614); 1,5-dicaffeoyl-3-maloylquinic acid, 1,4-dicaffeoyl-3-maloylquinic acid, and 1,5-dicaffeoyl-4-maloylquinic acid (Mr 632); 1,3,5-tricaffeoyl-4-succinoylquinic acid (Mr 778); 1,5-dicaffeoyl-3,4-disuccinoylquinic acid (Mr 716); 1,5-dicaffeoyl-3-fumaroyl-4-succinoylquinic acid and 1-fumaroyl-3,5-dicaffeoyl-4-succinoylquinic acid (Mr 714); dicaffeoyl-dimaloylquinic acid (Mr 748); and 1,5-dicaffeoyl-3-succinoyl-4-dimaloylquinic acid (Mr 732). All the structures have been assigned on the basis of LC-MSn patterns of fragmentation, relative hydrophobicity, and analogy of fragmentation patterns if compared to caffeoylquinic acids.
Co-reporter:Rakesh Jaiswal and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2011 Volume 59(Issue 8) pp:4033-4039
Publication Date(Web):March 17, 2011
DOI:10.1021/jf103545k
Arnica montana is a medicinally important plant due to its broad health effects, and it is used in Ayurvedic, Homeopathic, Unani, and folk medicines. We have used LC−MSn (n = 2−5) to detect and characterize in Arnica flowers 11 quantitatively minor fumaric and methoxyoxalic acid-containing chlorogenic acids, nine of them not previously reported in nature. These comprise 1,5-dicaffeoyl-3-methoxyoxaloylquinic acid, 1,3-dicaffeoyl-4-methoxyoxaloylquinic acid, 3,5-dicaffeoyl-4-methoxyoxaloylquinic acid, and 1-methoxyoxaloyl-4,5-dicaffeoylquinic acid (Mr 602); 3-caffeoyl-4-feruloyl-5-methoxyoxaloylquinic acid and 3-feruloyl-4-methoxyoxaloyl-5-caffeoylquinic acid (Mr 616); 1,5-dicaffeoyl-4-fumaroyl and 1,5-dicaffeoyl-3-fumaroylquinic acid (Mr 614); 3,5-dicaffeoyl-1,4-dimethoxyoxaloylquinic acid (Mr 688); and 1-methoxyoxaloyl-3,4,5-tricaffeoylquinic acid and 1,3,4-tricaffeoyl-5-methoxyoxaloylquinic acid (Mr 764). All of the structures have been assigned on the basis of LC−MSn patterns of fragmentation, relative hydrophobicity, and analogy of fragmentation patterns if compared to caffeoylquinic acids. This is the first time when fumaric acid-containing chlorogenic acids are reported in nature.
Co-reporter:Hande Karaköse, Rakesh Jaiswal, and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2011 Volume 59(Issue 18) pp:10143-10150
Publication Date(Web):August 2, 2011
DOI:10.1021/jf202185m
Stevia rebaudiana leaves are used as a zero-calorie natural sweetener in a variety of food products in Asian countries, especially in Japan. In this study, the hydroxycinnamate derivatives of S. rebaudiana have been investigated qualitatively and quantitatively by LC-MSn. Twenty-four hydroxycinnamic acid derivatives of quinic and shikimic acid were detected, and 19 of them were successfully characterized to regioisomeric levels; 23 are reported for the first time from this source. These comprise three monocaffeoylquinic acids (Mr 354), seven dicaffeoylquinic acids (Mr 516), one p-coumaroylquinic acid (Mr 338), one feruloylquinic acid (Mr 368), two caffeoyl-feruloylquinic acids (Mr 530), three caffeoylshikimic acids (Mr 336), and two tricaffeoylquinic acids (Mr 678). Cis isomers of di- and tricaffeoylquinic acids were observed as well. Three tricaffeoylquinic acids identified in stevia leaves are reported for the first time in nature. These phenolic compounds identified in stevia might affect the organoleptic properties and add additional beneficial health effects to stevia-based products.
Co-reporter:Nikolai Kuhnert, Rakesh Jaiswal, Pinkie Eravuchira, Rasha M. El-Abassy, Bernd von der Kammer and Arnulf Materny  
Analytical Methods 2011 vol. 3(Issue 1) pp:144-155
Publication Date(Web):15 Nov 2010
DOI:10.1039/C0AY00512F
Within this contribution we have analysed aqueous methanolic extracts by LC-ESI-TOF-MS of a total of 38 green bean coffee samples, which vary in terms of coffee variety and processing conditions. The LC-MS data have been analysed by principal component analysis (PCA) using different PCA processing parameters using an unsupervised non-targeted approach as well as a knowledge-based targeted approach. Furthermore, different normalisation and scaling algorithms have been applied to the PCA dataset. The scope and limitation of the various PCA parameters are discussed with respect to the ability to differentiate between samples of different groups, including different coffee varieties (Arabica or Robusta coffee) or different processing parameters and with respect to the information content of the PCA analysis on a molecular level. We could show that while distinction between different groups of samples can be successfully carried out independent of PCA parameters employed, identifying molecular markers rationalising differentiation between sample groups varies significantly between PCA parameters and requires careful choice as well as critical evaluation.
Co-reporter:Nikolai Kuhnert;Farnoosh Dairpoosh;Rakesh Jaiswal
Journal of Chemical Biology 2011 Volume 4( Issue 3) pp:109-116
Publication Date(Web):2011 July
DOI:10.1007/s12154-011-0055-9
Inspired by a recent article by Prinz, suggesting that Hill coefficients, obtained from four parameter logistic fits to dose–response curves, represent a parameter allowing distinction between a general allosteric denaturing process and real single site enzyme inhibition, Hill coefficients of a number of selected dietary polyphenol enzyme inhibitions were compiled from the available literature. From available literature data, it is apparent that the majority of polyphenol enzyme interactions reported lead to enzyme inhibition via allosteric denaturing rather than single site inhibition as judged by their reported Hill coefficients. The results of these searches are presented and their implications discussed leading to the suggestion of a novel hypothesis for polyphenol biological activity termed the insect swarm hypothesis.
Co-reporter:Rakesh Jaiswal, Joseph Kiprotich, Nikolai Kuhnert
Phytochemistry 2011 Volume 72(Issue 8) pp:781-790
Publication Date(Web):June 2011
DOI:10.1016/j.phytochem.2011.02.027
The hydroxycinnamates of the leaves of 12 plants of the Astreraceae family, Achillea millefolium, Arnica montana, Artemesia dracunculus, Cichorium intybus, Cnicus benedictus, Cynara scolymus, Echinops humilis, Inula helenium, Lactuca sativa, Petasites hybridus, Solidago virgaurea, and Tanacetum parthenium were investigated qualitatively by LC–MSn. Thirty-nine chlorogenic acids were detected and all characterized to regioisomeric level on the basis of their fragmentation pattern in the tandem MS spectra, most of them for the first time from these sources with two of them previously not reported in nature. Both chlorogenic acids based on trans and cis-cinnamic acid substituents were identified. Assignment to the level of individual regioisomers was possible for seven caffeoylquinic acids (1–7), 11 dicaffeoylquinic acids (17–27), six feruloylquinic acids (9–14), two p-coumaroylquinic acids (15–16), two caffeoyl–feruloylquinic acids (28 and 29), four caffeoyl-p-coumaroylquinic acids (30–33), three dicaffeoyl–succinoylquinic acids (34–36), two dicaffeoyl–methoxyoxaloylquinic acids (37 and 38), and one tricaffeoylquinic acid (39). Furthermore, one caffeoylshikimic acid (40), one caffeoyltartaric acid (41), three dicaffeoyltartaric acids (42–44), and three caffeoyl–feruloyltartaric acids (45–47) were detected and shown to possess characteristic tandem MS spectra and were tentatively assigned on the basis of their retention time and previously developed hierarchical keys.Graphical abstractFor the first time 1-p-coumaroyl-5-caffeoylquinic acid (30) and 1-p-coumaroyl-3-caffeoylquinic acid (33) are reported in nature and their regiochemistry is assigned by tandem mass spectrometry.Highlights► Chlorogenic acids and hydroxycinnamates based on cis and trans-cinnamic acids have identical MSn spectra. ► Chlorogenic acid regioisomers were easily distinguish by their characteristic tandem mass spectra. ► First time 1-p-coumaroyl-3-caffeoylquinic acid and 1-p-coumaroyl-3-caffeoylquinic acid were identified in nature.
Co-reporter:James Warren Drynan, Michael N. Clifford, Jacek Obuchowicz and Nikolai Kuhnert  
Natural Product Reports 2010 vol. 27(Issue 3) pp:417-462
Publication Date(Web):10 Feb 2010
DOI:10.1039/B912523J
Covering: 1930 to 2008
Co-reporter:Nikolai Kuhnert, Michael N. Clifford and Anja Müller  
Food & Function 2010 vol. 1(Issue 2) pp:180-199
Publication Date(Web):14 Oct 2010
DOI:10.1039/C0FO00066C
LC-MSn and direct infusion-MSn have been applied for the first time to the characterisation of crude thearubigins isolated from black tea. The data generated have been used to test two hypotheses of thearubigin structure: (i) that a significant fraction of the thearubigins consist of polyhydroxylated derivatives of the better-known catechin dimers (theaflavins, theaflavin mono- and di-gallates, theacitrins) in redox equilibrium with their associated quinones; and (ii) that a significant fraction of the thearubigins consist of dicarboxylic acids generated by oxidative cleavage of aromatic diols. The data were consistent with the polyhydroxylation hypothesis and did not support the dicarboxylic acid hypothesis. Evidence is presented for the presence in crude thearubigins of at least 29 hydroxylated theaflavins (with between one and six oxygen insertions), at least 12 theaflavin mono-gallates (with between one and six oxygen insertions), at least nine theaflavin di-gallates (with between one and four oxygen insertions), and at least ten theacitrin mono-gallates (with between one and four oxygen insertions). Evidence is also presented for at least ten mono- or di-quinone forms of the parent compounds and hydroxylated derivatives in each of these homologous series. A general method for the analysis of complex mixtures by tandem LC-MS is furthermore introduced and established.
Co-reporter:Rakesh Jaiswal, Tina Sovdat, Francesco Vivan and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2010 Volume 58(Issue 9) pp:5471-5484
Publication Date(Web):April 20, 2010
DOI:10.1021/jf904537z
The chlorogenic acids of maté (Ilex paraguariensis) have been investigated qualitatively by LC-MSn. Forty-two chlorogenic acids were detected and all characterized to regioisomeric level on the basis of their fragmentation pattern in tandem MS spectra, 24 of them for the first time from this source. Both chlorogenic acids based on trans- and cis-cinnamic acid substituents were identified. Assignment to the level of individual regioisomers was possible for eight caffeoylquinic acids (1−8), five dicaffeoylquinic acids (20−24), six feruloylquinic acids (9−14), two diferuloyl quinic acids (25 and 26), five p-coumaroylquinic acids (15−19), four caffeoyl-p-coumaroylquinic acids (34−37), seven caffeoyl-feruloylquinic acids (27−33), three caffeoyl-sinapoylquinic acids (38−40), one tricaffeoylquinic acid (41), and one dicaffeoyl-feruloylquinic acid (42). Furthermore, four caffeoylshikimates (43−46), three dicaffeoylshikimates (47−49), one tricaffeoylshikimate (51), and one feruloylshikimate (50) have been detected and shown to possess characteristic tandem MS spectra and were assigned by comparison to reference standards.
Co-reporter:Rakesh Jaiswal, Maria Alexandra Patras, Pinkie Jacob Eravuchira and Nikolai Kuhnert
Journal of Agricultural and Food Chemistry 2010 Volume 58(Issue 15) pp:8722-8737
Publication Date(Web):July 20, 2010
DOI:10.1021/jf1014457
LC-MSn (n = 2−4) has been used to detect and characterize in green Robusta coffee beans 15 quantitatively minor sinapic acid and trimethoxycinnamoylquinic acid-containing chlorogenic acids, all reported for the first time from this source, with 13 of them not previously reported in nature. These comprise 3-sinapoylquinic acid, 4-sinapoylquinic acid, and 5-sinapoylquinic acid (Mr 398); 3-sinapoyl-5-caffeoylquinic acid, 3-sinapoyl-4-caffeoylquinic acid, and 4-sinapoyl-3-caffeoylquinic acid (Mr 560); 3-(3,5-dihydroxy-4-methoxy)cinnamoyl-4-feruloylquinic acid (Mr 560); 3-sinapoyl-5-feruloylquinic acid, 3-feruloyl-4-sinapoylquinic acid, and 4-sinapoyl-5-feruloylquinic acid (Mr 574); 4-trimethoxycinnamoyl-5-caffeoylquinic acid, 3-trimethoxycinnamoyl-5-caffeoylquinic acid (Mr 574); and 5-feruloyl-3-trimethoxycinnamoylquinic acid, 3-trimethoxycinnamoyl-4-feruloylquinic acid, and 4-trimethoxycinnamoyl-5-feruloylquinic acid (Mr 588). Furthermore, a series of structures including nine new triacyl quinic acids have been assigned on the basis of LC-MSn patterns of fragmentation, relative hydrophobicity, and analogy of fragmentation patterns if compared to feruloyl, caffeoyl, and dimethoxycinnamoyl quinic acids. Sixty-nine chlorogenic acids have now been characterized in green Robusta coffee beans.
Co-reporter:Nikolai Kuhnert, David Marsh, Daniel C. Nicolau
Tetrahedron: Asymmetry 2007 Volume 18(Issue 14) pp:1648-1654
Publication Date(Web):30 July 2007
DOI:10.1016/j.tetasy.2007.07.011
Co-reporter:Nikolai Kuhnert
Archives of Biochemistry and Biophysics (1 September 2010) Volume 501(Issue 1) pp:37-51
Publication Date(Web):1 September 2010
DOI:10.1016/j.abb.2010.04.013
Co-reporter:
Analytical Methods (2009-Present) 2012 - vol. 4(Issue 3) pp:
Publication Date(Web):
DOI:10.1039/C2AY05249K
A novel direct-infusion atmospheric pressure chemical ionization mass spectrometry method to identify saturated straight-chain hydrocarbons in light shredder waste fraction has been developed. Ionization of alkanes under nitrogen gas source favored hydrogen abstraction producing mostly (M–H)+ ions, which strictly correspond to their respective series of n-alkanes between n-decane (C10) and n-tetra-contane (C40). The method is shown to produce intact gas phase ions of n-alkane in both reference and real life waste samples. APCI-MS2 fragmentation data assisted in the structural verification of the n-alkanes investigated in both standard and waste mixtures.
Co-reporter:Hany F. Nour, Nadim Hourani and Nikolai Kuhnert
Organic & Biomolecular Chemistry 2012 - vol. 10(Issue 22) pp:NaN4389-4389
Publication Date(Web):2012/04/03
DOI:10.1039/C2OB25171J
A total of twelve novel enantiomerically pure tetra-carbohydrazide cyclophane macrocycles have been synthesised in quantitative yields by reacting chiral (4R,5R)- and (4S,5S)-1,3-dioxolane-4,5-dicarbohydrazides with aromatic bis-aldehydes in a [2+2]-cyclocondensation reaction. The compounds show a dynamic behaviour in solution, which has been rationalized in terms of an unprecedented conformational interconversion between two conformers one stabilised by intramolecular hydrogen bonding and π–π stacking interactions.
Co-reporter:
Analytical Methods (2009-Present) 2014 - vol. 6(Issue 10) pp:
Publication Date(Web):
DOI:10.1039/C3AY41970C
In this contribution we have analysed aqueous methanolic extracts of a total of 38 green bean coffee samples, which vary in terms of the coffee variety and processing conditions. We have characterised these extracts using NMR-, IR- and CD-spectroscopies along with LC-MS. All spectroscopic data have been analysed by principal component analysis (PCA) using different PCA processing parameters by an unsupervised non-targeted approach. We could show that the distinction between different groups of samples, in particular, Arabica versus Robusta green coffee beans can be successfully analysed by IR-spectroscopy and LC-MS. Surprisingly both CD- and NMR-spectroscopies fail to achieve, in this case, an adequate level of distinction. This is, to the best of our knowledge, the first study that directly compares the value of various spectroscopic techniques if multivariant statistical techniques are employed to them.
Co-reporter:Nikolai Kuhnert, Rakesh Jaiswal, Pinkie Eravuchira, Rasha M. El-Abassy, Bernd von der Kammer and Arnulf Materny
Analytical Methods (2009-Present) 2011 - vol. 3(Issue 1) pp:
Publication Date(Web):
DOI:10.1039/C0AY00512F
Co-reporter:Rakesh Jaiswal, Michael H. Dickman and Nikolai Kuhnert
Organic & Biomolecular Chemistry 2012 - vol. 10(Issue 27) pp:NaN5277-5277
Publication Date(Web):2012/05/11
DOI:10.1039/C2OB25124H
We report on a diastereoselective synthesis of six derivatives of caffeoyl- and feruloyl-muco-quinic acids. All the muco-quinic acid derivatives were obtained in excellent yield in five steps starting from quinic acid, caffeic acid and ferulic acid. Allyl ether protection of trans-hydroxy cinnamic acids was here introduced to chlorogenic acids synthesis. We show that muco-quinic acid derivatives, which are formally diastereoisomers of chlorogenic acids, can be readily distinguished by their tandem mass spectra
Co-reporter:Hany F. Nour, Marius F. Matei, Bassem S. Bassil, Ulrich Kortz and Nikolai Kuhnert
Organic & Biomolecular Chemistry 2011 - vol. 9(Issue 9) pp:NaN3271-3271
Publication Date(Web):2011/03/23
DOI:10.1039/C0OB00944J
2-Functionalised aromatic monoaldehydes were synthesised in good to excellent yields by reacting 4-bromo-2-fluorobenzaldehyde with different secondary amines and phenol. The Suzuki-coupling reaction of the newly functionalised aromatic monoaldehydes with 4-formylphenylboronic acid afforded the corresponding 2-functionalised-4,4′-biphenyldialdehydes in good yields (47–85%). The [3+3]-cyclocondensation reactions of the 2-functionalised-4,4′-biphenyldialdehydes with (1R,2R)-1,2-diaminocyclohexane afforded a mixture of regioisomeric C3-symmetrical and non-symmetrical trianglimines. Reduction of the C3-symmetrical and the non-symmetrical trianglimines with NaBH4 in a mixture of THF and MeOH afforded the corresponding trianglamines in high yields.
4-cis-feruloylquinic acid
guaijaverin
Zanamivir
kaempferol 3-alpha-rhamnopyranoside-7-beta-xylopyranoside
3-caffeoylquinic acid methyl ester
1-(3,7-Dihydroxy-10H-phenoxazin-10-yl)ethanone
3-O-beta-D-Glucopyranoside-(2R,3S)-3,3',4',5,7-Pentahydroxyflavan
(+)-catechin 8-C-beta-D-glucopyranoside
2-Propenoyl chloride, 3-[3,4-bis(acetyloxy)phenyl]-, (2E)-