Mechanistic insights into furan formation in Maillard model systems

Furan has recently received considerable attention as a possibly carcinogenic compound occurring in thermally processed foods. Although several food constituents have been identified as furan precursors, multiple formation pathways remain unclear. Therefore, the mechanisms of furan formation in Maillard model systems were studied by means of the carbon module labeling (CAMOLA) technique. Under both roasting and pressure-cooking conditions, furan was formed from glucose via the intact skeleton, and its formation pathways from glucose alone were not amino acid-dependent. However, some amino acids, especially alanine and serine, did influence the furan production by providing an additional formation pathway. Furthermore, most amino acids enhanced the furan production from glucose. Roasting conditions produced 25-100 times higher amounts of furan as compared to pressure-cooking conditions. Surprisingly, in the alanine/glucose model systems, the relative importance of furan production from glucose alone and from the combination of a glucose-derived and an alanine-derived fragment changed completely over a limited time course of 60 min.     

Origin and mechanistic pathways of formation of the parent furan--a food toxicant

Studies performed on model systems using pyrolysis-GC-MS analysis and (13)C-labeled sugars and amino acids in addition to ascorbic acid have indicated that certain amino acids such as serine and cysteine can degrade and produce acetaldehyde and glycolaldehyde that can undergo aldol condensation to produce furan after cyclization and dehydration steps. Other amino acids such as aspartic acid, threonine, and alpha-alanine can degrade and produce only acetaldehyde and thus need sugars as a source of glycolaldehyde to generate furan. On the other hand, monosaccharides are also known to undergo degradation to produce both acetaldehyde and glycolaldehyde; however, (13)C-labeling studies have revealed that hexoses in general will mainly degrade into the following aldotetrose derivatives to produce the parent furan-aldotetrose itself, incorporating the C3-C4-C5-C6 carbon chain of glucose (70%); 2-deoxy-3-ketoaldotetrose; incorporating the C1-C2-C3-C4 carbon chain of glucose (15%); and 2-deoxyaldotetrose, incorporating the C2-C3-C4-C5 carbon chain of glucose (15%). Furthermore, it was also proposed that under nonoxidative conditions of pyrolysis, ascorbic acid can generate the 2-deoxyaldotetrose moiety, a direct precursor of the parent furan. In addition, 4-hydroxy-2-butenal-a known decomposition product of lipid peroxidation-was proposed as a precursor of furan originating from polyunsaturated fatty acids. Among the model systems studied, ascorbic acid had the highest potential to produce furan, followed by glycolaldehyde/alanine > erythrose > ribose/serine > sucrose/serine > fructose/serine > glucose/cysteine.     

Roasting effects on formation mechanisms of coffee brew melanoidins

The effect of the roasting degree on coffee brew melanoidin properties and formation mechanisms was studied. Coffee brew fractions differing in molecular weight (Mw) were isolated from green and light-, medium-, and dark-roasted coffee beans. Isolated fractions were characterized for their melanoidin, nitrogen, protein, phenolic groups, chlorogenic acid, quinic acid, caffeic acid, and sugar content. It was found that the melanoidin level in all fractions correlated with both the nitrogen and the protein content. The melanoidin level also correlated with the phenolic groups' level and ester-linked quinic acid level. It was concluded that proteins and chlorogenic acids should be primarily involved in melanoidin formation. Initial roasting, from green to light-roasted beans, especially led to the formation of intermediate Mw (IMw) melanoidins when compared to high Mw (HMw) melanoidins. Indications were found that this IMw melanoidin formation is mainly due to Maillard reactions and chlorogenic acid incorporation reactions between chlorogenic acids, sucrose, and amino acids/protein fragments. Additionally, it was found that prolonged roasting predominantly led to formation melanoidins with a high Mw. Furthermore, arabinogalactans seem to be relatively more involved in melanoidin formation than galactomannans. It was hypothesized that chromophores may be formed or attached through the arabinose moiety of arabinogalactan proteins (AGP). Finally, it could be concluded that galactomannans are continuously incorporated in AGP-melanoidins upon roasting.     

Intact carbohydrate structures as part of the melanoidin skeleton

Model melanoidins from monomeric, oligomeric, and polymeric carbohydrates, and amino acids formed under aqueous as well as water-free reaction conditions, were submitted to acidic catalyzed hydrolysis. Their degradation products were detected qualitatively and quantitatively by HPTLC and HPLC-DAD. A considerable amount of monomer carbohydrates from hydrolysis of model melanoidins formed under water-free reaction conditions was detected. It can be seen clearly that the amount of carbohydrates released increased with increasing degree of polymerization of the carbohydrates used as starting material. In comparison, the hydrolysis of melanoidins formed in aqueous condition resulted in only a small glucose release. It seems that in the Maillard reaction under water-free conditions, a significant amount of di- and oligomer carbohydrates were incorporated into the melanoidin skeleton as complete oligomer with intact glycosidic bond, forming side chains at the melanoidin skeleton. Additional side chains could be formed by transglycosylation reactions. With increasing water content, hydrothermolytic as well as retro-aldol reactions of the starting carbonyl components became significant, and therefore the possibility of forming side chains decreased. The results are consistent with the postulated melanoidin structure being built up mainly from sugar degradation products, probably branched via amino compounds.     

Reactivity of epicatechin in aqueous glycine and glucose maillard reaction models: quenching of C2, C3, and C4 sugar fragments

Mechanisms of how epicatechin alters the pathways of the Maillard reaction were investigated. Carbon-13 and nitrogen-15 labeling studies were utilized to define the reactivity of epicatechin with glucose, glycine, and/or reaction products in an aqueous model (pH 7, 125 degrees C for 30 min) via GC, GC/MS and HPLC/MS analysis. Quantification of the volatile reaction product isotopomers by GC/MS from a 1:1 labeled to unlabeled glucose (carbohydrate module labeling technique) plus glycine model system indicated the formation of 2,3-butanedione and acetol were primarily formed via intact C4 and C3 sugar fragments, whereas pyrazine, methylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, and cyclotene were primarily formed via intact C2/C2, C2/C3, C3/C3, C3/C3, and C3/C3 sugar fragment pairs, respectively. The formation of these seven compounds was also reported by GC analysis to be dramatically inhibited when epicatechin was added to the glucose/glycine model system (observed 9-113-fold reduction). HPLC/MS analysis of both the glucose-labeled and glycine-labeled model systems with and without epicatechin indicated that epicatechin reacted directly with C2, C3, and C4 sugar fragments, while epicatechin did not report any direct reactivity with glycine. In conclusion, the quenching of sugar fragmentation products via epicatechin was correlated with the observed inhibition on volatile compound formation when epicatechin was added to a glucose/glycine aqueous reaction model system.     

Intestinal absorption of p-coumaric and gallic acids in rats after oral administration

Ferulic acid (FA) and p-coumaric acid (CA) are absorbed by the monocarboxylic acid transporter (MCT) in Caco-2 cells, although gallic acid (GA) is not. Therefore, the MCT is selective for certain phenolic acids. Absorption of orally administered CA and GA in rats was studied to obtain serum pharmacokinetic profiles and to investigate their intestinal absorption characteristics in vivo. Rats were administered 100 micromol/kg body weight of CA and GA, and blood was collected from the portal vein and abdominal artery after administration. CA, GA, and their metabolites were quantified with a highly selective and sensitive coulometric detection method using high-performance liquid chromatography-electrochemical detection. Ingested CA was rapidly absorbed in the gastrointestinal tract in an intact form. The serum concentration of intact CA in the portal vein peaked 10 min after dosing (C(max) was 165.7 micromol/L). In contrast, GA was slowly absorbed, with a t(max) for intact GA of 60 min and a C(max) of 0.71 micromol/L. The area under the curve for intact CA and GA was calculated from the serum concentration profile in the portal vein to be 2991.3 and 42.6 micromol min L(-)(1), respectively. The relative bioavailability of CA against GA was about 70. This is the first demonstration that absorption efficiency of CA is much higher than that of GA in vivo. The absorption characteristics of CA are clearly different from those of GA. These findings are in good agreement with the results obtained in vitro using a Caco-2 cell system.     

母质对新形成腐殖质的影响

本文研究了在旱地和水田条件下,母质对新形成腐殖质的影响.供试物料为紫云英、绿萍、稻草和水葫芦.结果表明:1.除绿萍外,各物料腐解三年后均已分解较完全.腐解产物的C/有机N值和腐殖质组成均随原始物料而异.2.当植物物料和母质相同时,与水田条件下的相比,旱地条件下的腐解产物的C/有机N值大多较窄,中性糖量较高,六碳糖/五碳糖值较宽,腐殖酸的提取率较高.3.当水分条件和植物物料相同时,与第四纪红色粘土中的相比,下蜀黄土中腐解产物的胡敏酸的C/N值大多较窄,六碳糖/五碳糖值和胡敏酸/富里酸值大多较宽.作者认为,二者中腐殖质组成的差别在一定程度上系由于粘土矿物的组成不同所致.     

Acrylamide in roasted almonds and hazelnuts

The influences of composition and roasting conditions on acrylamide formation in almonds and hazelnuts were investigated. Eighteen samples of almonds originating from the U.S. and Europe were analyzed for sugars and free amino acids, and acrylamide formed during roasting was determined. Asparagine was the main free amino acid in raw almonds and correlated with the acrylamide content of dark roasted almonds. Roasting temperature was another key factor and had a very strong influence on acrylamide formation. Almonds of European origin contained significantly less free asparagine and formed significantly less acrylamide during roasting as compared to the almonds from the U.S. Roasted hazelnuts contained very little acrylamide because of the low content of free asparagine in the raw nut. Reducing sugars, although being consumed much faster than free amino acids in both types of nuts, were not decisive for the extent of acrylamide formation during roasting.     

Changes in green coffee protein profiles during roasting

To reveal its flavor, coffee has to be roasted. In fact, the green coffee bean contains all ingredients necessary for the later development of coffee flavor. It is now widely accepted that free amino acids and peptides are required for the generation of coffee aroma. However, the mechanisms leading to defined mixtures of free amino acids and peptides remain unknown. Information pertaining to the identification of precursor proteins is also lacking. To answer some of these questions, two-dimensional polyacrylamide gel electrophoresis (2D-PAGE) was used to follow the fate of green coffee proteins. Two conditions were considered: roasting and incubation of green coffee suspensions at 37 degrees C. Coffee beans were observed to acquire the potential to spontaneously release H(2)O(2) upon polymerization of their proteins during roasting. Fragmentation of proteins was also observed. Conversely, H(2)O(2) was found to control polymerization and fragmentation of green coffee proteins in solution at 37 degrees C. Polymerization and fragmentation patterns under the two conditions were comparable. These observations suggest that the two conditions under study triggered, at least to some extent, similar biochemical mechanisms involving autoxidation. Throughout this study, a unique fragmentation cascade involving the 11S coffee storage protein was identified. Generated fragments shared an atypical staining behavior linked to their sensitivity to redox conditions.     

Retention of essential amino acids during extrusion of protein and reducing sugars

This research investigates the retention of essential amino acid profiles of products during the extrusion of proteins and reducing sugars. Animal proteins (egg and milk protein at 10 and 30% levels) and reducing sugars (fructose and galactose at 0, 2, and 8% levels), with pregelatinized wheat flour, were extruded at 110 and 125 degrees C product temperatures and feed moistures of 19 and 23.5% for egg protein and 13.75 and 16% for milk protein. The nutritional property analyzed was essential amino acid retention, and sugar retention was also considered to understand the relationship of sugars with retention of amino acids. Lysine showed the lowest retention (up to 40%) of all the essential amino acids. Retention of other essential amino acids varied from 80 to 100% in most situations. Apart from lysine, tryptophan, threonine, and methionine were found to be significantly changed ( P < 0.05) with processing conditions. Increased protein and sugar levels resulted in a significant degradation of lysine. Greater lysine retention was found at a lower temperature and higher feed moisture. Results of sugar retention also showed similar patterns. The products made from fructose had greater lysine retention than products made from galactose with any type of protein. The outcomes of this research suggested that the combination of milk protein and fructose at a lower temperature and higher feed moisture is most favorable for developing high-protein extruded products.     

大气CO2浓度升高和氮肥互作对玉米花后功能叶碳氮同化物的影响

在常规大气CO2浓度（aCO2，400±15μmol·mol−1）和高CO2浓度（eCO2，550±20μmol·mol−1）下分别设置无氮（ZN）和施氮（CN，180kg N·hm−2）2个氮水平的交互处理，以夏玉米品种郑单958为供试材料开展田间试验，测定花后功能叶碳同化物（可溶性糖和淀粉、总碳）动态和氮吸收及同化物组分（硝态氮、游离氨基酸、可溶性蛋白、非溶性氮化合物细胞壁氮素和类囊体氮素、总氮）动态以及碳氮比动态的变化及玉米产量，以探究CO2浓度升高和氮肥交互作用下，以玉米为代表的C4作物花后功能叶不同组分碳氮同化物质量分数及动态和产量的变化，以期为全球气候变化下玉米生理过程的变化提供理论支撑，同时为玉米作物模型调参提供实证数据。结果表明：（1）本试验条件下，大气CO2浓度升高对夏玉米生物量及产量的作用不显著。（2）eCO2下夏玉米花后功能叶主要碳同化产物（可溶性糖和淀粉）和总碳的质量分数显著（P＜0.05）增加，功能叶中氮同化物中简单组分（硝态氮、游离氨基酸及可溶性蛋白）质量分数和碳氮比、地上部生物量、产量也有一定增加，但未达显著水平；而氮同化物中的结构氮组分（如细胞壁氮和类囊体氮）质量分数显著降低，总氮也有一定降低趋势，显示出后期结构氮组分合成有一定不足。（3）氮肥施用显著增加了花后功能叶碳同化物（如可溶性糖和大部分时期淀粉）及各种氮同化物的质量分数和生物量及产量，对总碳的增加作用不显著。（4）eCO2下合理施用氮肥，会使地上部生物量、产量、功能叶中简单碳同化物可溶性糖、简单氮同化物指标（硝态氮、游离氨基酸和可溶性蛋白）和总碳质量分数达到较优。因此，在未来大气CO2浓度升高为特征之一的气候变化背景下，氮素合成的生理调控管理对促进碳氮代谢及玉米高产优质有积极作用。     

A GC/MS method for the assessment of N and C incorporation into soil amino acid enantiomers

Identifying the transformation process of amino acid enantiomers was essential to probe into the fate, turnover and aging of soil nitrogen due to their important roles in the biogeochemical cycling. If this can be achieved by differentiating between the newly biosynthesized and the inherent compounds in soil, then the isotope tracer method can be considered most valid. We thereby developed a gas chromatography/mass spectrometry (GC/MS) method to trace the ¹⁵N or ¹³C isotope incorporation into soil amino acid enantiomers after being incubated with ¹⁵NH₄⁺ or U-¹³C-glucose substrates. The most significant fragments (F) as well as the related minor ions were monitored by the full scan mode and the isotope enrichment in amino acids was estimated by calculating the atom percentage excess (APE). ¹⁵NH₄⁺ incorporation was evaluated according to the relative abundance increase of m/z F+1 to F for neutral and acidic amino acids and F+2 to F (mass 439) for lysine. The assessment of ¹³C enrichment in soil amino acids was more complicated than that of ¹⁵N due to multi-carbon atoms in amino acid molecules. The abundance ratio increment of m/z F+n to F (n is the original skeleton carbon number in each fragment) indicated the direct conversion from the added glucose to amino acids, but the total isotope incorporation from the added ¹³C can only be calculated according to all target isotope fragments, i.e. the abundance ratio increment summation from m/z (Fa+1) through m/z (Fa+T) represented the total incorporation of the added ¹³C (Fa is the fragment containing all original skeleton carbons and T is the carbon number in the amino acid molecule). This method has a great advantage especially for the evaluation of high-abundance isotope enrichment in organic compounds compared with GC/C/IRMS. And in principle, this technique is also valid for amino acids besides enantiomers if stereoisomers are not concerned. Our assessment approach could shine a light on investigating the biochemical mechanism of microbial transformation of N and C in soils of terrestrial ecosystem.     

Factors affecting thermally induced furan formation

Furan, a potential carcinogen, can be induced by heat from sugars, ascorbic acid, and fatty acids. The objective of this research was to investigate the effect of pH, phosphate, temperature, and heating time on furan formation. Heat-induced furan formation from free sugars, ascorbic acid, and linoleic acid was profoundly affected by pH and the presence of phosphate. In general, the presence of phosphate increased furan formation in solutions of sugars and ascorbic acid. In a linoleic acid emulsion, phosphate increased the formation of furan at pH 6 but not at pH 3. When an ascorbic acid solution was heated, higher amounts of furan were produced at pH 3 than at pH 6 regardless of phosphate's presence. However, in linoleic acid emulsion, more furan was produced at pH 6 than at pH 3. The highest amount of furan was formed from the linoleic acid emulsion at pH 6. In fresh apple cider, a product with free sugars as the major components (besides water) and little fatty acids, ascorbic acid, or phosphate, small or very low amounts of furan was formed by heating at 90-120 degrees C for up to 10 min. The results indicated that free sugars may not lead to significant amounts of furan formation under conditions for pasteurization and sterilization. Importantly, this is the first report demonstrating that phosphate (in addition to pH) plays a significant role in thermally induced furan formation.     

Quantitative precursor studies on di- and trihydroxybenzene formation during coffee roasting using "in bean" model experiments and stable isotope dilution analysis

The objective of this study was to investigate the potential of various raw bean components as precursors of pyrogallol (1), hydroxyhydroquinone (2), catechol (3), 4-ethylcatechol (4), 4-methylcatechol (5), and 3-methylcatechol (6) under quasi "natural" roasting conditions by using the recently developed "in bean" model roast experiments. Freeze-dried, fully extracted bean shells were loaded with aqueous solutions of either single coffee compounds or fractions isolated from the raw bean solubles. After freeze-drying, these reconstituted beans were roasted, aqueous coffee brews were prepared, and the target phenols were quantified by means of a stable isotope dilution assay with LC-MS/MS detection. On the basis of the quantitative data, it can be concluded that upon coffee bean roasting, catechol (3) is primarily formed by degradation of caffeoylquinic acids from both the caffeic acid and the quinic acid moiety of the molecule, as well as from Maillard-type reactions from carbohydrates and amino acids. In contrast, pyrogallol (1) and hydroxyhydroquinone (2) are efficiently generated from carbohydrates and amino acids and, in addition, from free or chlorogenic acid bound quinic acid moieties. 4-Ethylcatechol (4) is exclusively generated upon thermal breakdown of caffeic acid moieties. 3-Methylcatechol (6) is formed primarily from the Maillard reactions and, to a minor extent, also from various phenolic precursors, whereas 4-methylcatechol (5) is produced in trace amounts only from all of the different precursors investigated. On the basis of this precursor study, reaction routes explaining the formation of the target phenols are proposed.     

Formation of aroma compounds from ribose and cysteine during the Maillard reaction

The headspace volatiles produced from a phosphate-buffered solution (pH 5) of cysteine and a 1 + 1 mixture of ribose and [(13)C(5)]ribose, heated at 95 degrees C for 4 h, were examined by headspace SPME in combination with GC-MS. MS data indicated that fragmentation of ribose did not play a significant role in the formation of the sulfur aroma compounds 2-methyl-3-furanthiol, 2-furfurylthiol, and 3-mercapto-2-pentanone in which the carbon skeleton of ribose remained intact. The methylfuran moiety of 2-methyl-3-(methylthio)furan originated from ribose, whereas the methylthio carbon atoms came partly from ribose and partly from cysteine. In 3-mercapto-2-butanone one carbon unit was split from the ribose chain. On the other hand, all carbon atoms in 3-thiophenethiol stemmed from cysteine. In another trial cysteine, 4-hydroxy-5-methyl-3(2H)-furanone and [(13)C(5)]ribose were reacted under the same conditions. The resulting 2-methyl-3-furanthiol was mainly (13)C(5)-labeled, suggesting that it stems from ribose and that 4-hydroxy-5-methyl-3(2H)-furanone is unimportant as an intermediate. Whereas 2-mercapto-3-pentanone was found unlabeled and hence originated from 4-hydroxy-5-methyl-3(2H)-furanone, its isomer 3-mercapto-2-pentanone was formed from both 4-hydroxy-5-methyl-3(2H)-furanone and ribose. A new reaction pathway from ribose via its 1,4-dideoxyosone is proposed, which explains both the formation of 2-methyl-3-furanthiol without 4-hydroxy-5-methyl-3(2H)-furanone as an intermediate and a new way to form 3-mercapto-2-pentanone.     

Determination of acrylamide during roasting of coffee

In this study different Arabica and Robusta coffee beans from different regions of the world were analyzed for acrylamide after roasting in a laboratory roaster. Due to the complex matrix and the comparably low selectivity of the LC-MS at m/ z 72, acrylamide was analyzed after derivatization with 2-mercaptobenzoic acid at m/ z 226. Additionally, the potential precursors of acrylamide (3-aminopropionamide, carbohydrates, and amino acids) were studied. The highest amounts of acrylamide formed in coffee were found during the first minutes of the roasting process [3800 ng/g in Robusta ( Coffea canephora robusta) and 500 ng/g in Arabica ( Coffea arabica)]. When the roasting time was increased, the concentration of acrylamide decreased. It was shown that especially the roasting time and temperature, species of coffee, and amount of precursors in raw material had an influence on acrylamide formation. Robusta coffee contained significantly larger amounts of acrylamide (mean = 708 ng/g) than Arabica coffee (mean = 374 ng/g). Asparagine is the limiting factor for acrylamide formation in coffee. 3-Aminopropionamide formation was observed in a dry model system with mixtures of asparagine with sugars (sucrose, glucose). Thermal decarboxylation and elimination of the alpha-amino group of asparagine at high temperatures (>220 degrees C) led to a measurable but low formation of acrylamide.     

Formation of amines and aldehydes from parent amino acids during thermal processing of cocoa and model systems: new insights into pathways of the strecker reaction

A method based on a derivatization with dansyl chloride and LC-MS-MS determination was developed for the quantitation of 2-methylbutyl-, 3-methylbutyl-, 2-phenylethyl-, 3-(methylthio)propyl-, and 2-methylpropylamine. Its application on unfermented, fermented, and roasted cocoas from Ghana and Sulawesi revealed an increase of all amines, except the 3-(methylthio)propylamine, during cocoa fermentation, suggesting an enzymic formation from the parent amino acids isoleucine, leucine, phenylalanine, and valine. However, a much more pronounced formation of most of the amines was measured after roasting of the cocoa, leading to concentrations in the milligrams per kilogram range. This result suggested a new "thermogenic" formation pathway of "biogenic amines". A comparison of the amounts of the amines and the aldehydes in roasted cocoa revealed similar concentrations, for example, for 2- and 3-methylbutanal and the respective amines, whereas the amounts of 2-phenylethylamine were much higher as compared to the amounts of phenylacetaldehyde. Strecker-type model systems, in which each parent amino acid was reacted with 2-oxopropanal, revealed the formation of both the amine and the aldehyde; however, in contrast to cocoa, the concentrations of the aldehydes were always much higher as compared to the amines. The results showed for the first time the thermally induced generation of "biogenic amines" from amino acids. Possible reasons for the different ratios of amines versus aldehydes formed during the roasting of cocoa or the model systems, respectively, are discussed.     

Structure determination of a novel 3(6H)-pyranone chromophore and clarification of its formation from carbohydrates and primary amino acids

An intensely orange compound, which has recently been evaluated as one of the main colored compounds formed in Maillard reactions of hexoses, could be unequivocally identified as (Z)-2-[(2-furyl)methylidene]-5,6-di(2-furyl)-6H-pyran-3-one (1) by application of several NMR and LC-MS experiments. To clarify its formation, the effectiveness of certain carbohydrate degradation products as precursors of 1 was studied in a quantitative experiment demonstrating hydroxy-2-propanone, furan-2-aldehyde, and 3-deoxy-2-hexosulose as precursors of the colorant. Site-specific labeling experiments with D-1-[(13)C]glucose and D-6-[(13)C]glucose, respectively, were performed to elucidate the formation pathway of 1 involving a cleavage of the hexose skeleton between carbon atoms C(5) and C(6). In addition, pentoses could be shown to generate 1 via a similar formation pathway involving the 3-deoxy-2-pentosulose.     

Influence of epicatechin reactions on the mechanisms of Maillard product formation in low moisture model systems

The influence of the polyphenolic compound epicatechin on Maillard chemistry was investigated under simulated roast conditions (10% moisture at 220 degrees C for 10 min). Quantitative gas chromatography (GC) analysis indicated that the addition of epicatechin to glucose or fructose/glycine model systems significantly reduced the generation of hydroxyacetone, 2-methylpyrazine, 2,3,5-trimethylpyrazine, furfural, 2-acetylfuran, 5-methylfurfural, 2(5H)-furanone, 2-acetylpyrrole, and furfuryl alcohol. These analytes were reported to be primarily generated from intact C2, C3, C4, C5, and C6 sugar fragments based on gas chromatography/mass spectrometry quantitative isotopomeric analysis of a 1:1 13C6:12C6 hexose sugar/glycine model system. Liquid chromatography/mass spectrometry qualitative isotopomeric analysis of a 1:1 13C6:12C6 hexose sugar/glycine/epicatechin model systems confirmed epicatechin reacted with Maillard reactants in the model systems; two main reaction products were reported, epicatechin-C5 and -C6 sugar fragment adducts. In addition, LC/MS analysis of a model system consisting of only 3-deoxy-2-hexosulose and epicatechin identified 3-deoxy-2-hexosulose as a precursor of the epicatechin-C5 and -C6 sugar fragment adducts reaction products. These results imply that epicatechin quenched 3-deoxy-2-hexosulose (a key source C6 to C1 sugar fragments) and consequently inhibited Maillard product formation.     

Molecular composition of humic substances in tundra soils (13C-NMR spectroscopic study)

Functional groups and molecular fragments of humic substances (HSs) from cryohydromorphic peat gley tundra and surface-gley tundra soils have been identified by ¹³C-NMR spectroscopy. The analysis of HS preparations has shown that the molecules of humic acids (HAs) are enriched with aromatic fragments compared to fulvic acids (FAs). Aliphatic chains, carbohydrate- and amino acid-type structures prevail in the carbon skeleton of the FAs. An integrated parameter of the HS hydrophobicity has been proposed. The parameter represents the total portion of unoxidized carbon atoms and allows indirectly assessing the amphiphilic properties of HSs.