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1.
Pyrazine formation from serine and threonine.   总被引:4,自引:0,他引:4  
The formation of pyrazines from L-serine and L-threonine has been studied. L-Serine and L-threonine, either alone or combined, were heated at 120 degrees C as low temperature for 4 h or at 300 degrees C as high temperature for 7 min. The pyrazines formed from each reaction were identified by GC/MS, and the yields (to the amino acid used, as parts per million) were determined by GC/FID. It was found that pyrazine, methylpyrazine, ethylpyrazine, 2-ethyl-6-methylpyrazine, and 2,6-diethylpyrazine were formed from serine, whereas 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, trimethylpyrazine, 2-ethyl-3,6-dimethylpyrazine, and 2-ethyl-3, 5-dimethylpyrazine were formed from threonine. Mechanistically, it is proposed that the thermal degradation of serine or threonine is composed of various complex reactions. Among these reactions, decarbonylation followed by dehydration is the main pathway to generate the alpha-aminocarbonyl intermediates leading to the formation of the main product, such as pyrazine from serine or 2, 5-dimethylpyrazine from threonine. Also, deamination after decarbonylation generates more reactive intermediates, alpha-hydroxycarbonyls. Furthermore, aldol condensation of these reactive intermediates provides alpha-dicarbonyls. Subsequently, these alpha-dicarbonyls react with the remaining serine or threonine by Strecker degradation to form additional alpha-aminocarbonyl intermediates, which then form additional pyrazines. In addition, decarboxylation and retroaldol reaction may also involve the generation of the intermediates.  相似文献   

2.
Sugars and amino acids were removed from potato slices by soaking in water and ethanol. They were then infused with various combinations of sugars (glucose and/or fructose) and amino acids (asparagine, glutamine, leucine, isoleucine, phenylalanine, and/or methionine) and fried. Volatile compounds were trapped onto Tenax prior to gas chromatography-mass spectrometry. Relative amounts of compounds (relative to the internal standard) and relative yields (per mole of amino acid infused into the slices) were determined. Amounts of 10 pyrazines, 4 Strecker aldehydes, and 4 other compounds were monitored. Relative amounts and relative yields of compounds varied according to the composition of the system. For the single amino acid-glucose systems, leucine gave the highest relative amount and relative yield of its Strecker aldehyde. Asparagine and phenylalanine gave the highest total relative amount and total relative yield, respectively, of pyrazines. In the system containing all of the amino acids and glucose, the relative amount of 3-methylbutanal was higher, whereas the amounts of the other monitored Strecker aldehydes were lower. Most of the relative amounts of individual pyrazines were lower compared to the glucose-asparagine system, whereas the total relative yield of pyrazines was lower, compared to all of the single amino acid-glucose mixtures. Addition of fructose to the mixed amino acid-glucose model system generated Strecker aldehydes and pyrazines in ratios that were more similar to those of untreated potato chips than to those from the same system but without fructose. Both the sugars and the amino acids present in potato are crucial to the development of flavor compounds in fried potato slices.  相似文献   

3.
The formation of furan and 2-methylfuran was studied in model systems based on sugars and selected amino acids. Both compounds were preferably formed under roasting conditions in closed systems yielding up to 330 micromol of furan and 260 micromol of 2-methylfuran per mol of precursor. The amounts obtained under pressure cooking conditions were much lower, usually below 20 micromol/mol, except for 2-furaldehyde, which yielded 70-100 micromol/mol of furan. Labeling studies indicated two major formation pathways for both furans: (i) from the intact sugar skeleton and (ii) by recombination of reactive C(2) and/or C(3) fragments. Under roasting conditions in the absence of amino acids, furan was mainly formed from the intact sugar skeleton. Formic and acetic acid were identified as byproducts of sugar degradation, indicating the split off of C(1) and/or C(2) units from hexoses. The presence of alanine, threonine, or serine promoted furan formation by the recombination of C(2) fragments, such as acetaldehyde and glycolaldehyde, which may originate from both sugars and amino acids. In aqueous solution, about half of furan was generated by the recombination of sugar fragments. 2-Methylfuran was preferably formed in the presence of amino acids by aldol-type reactions of C(2) and C(3) fragments with lactaldehyde as a key intermediate, the Strecker aldehyde of threonine. The total furan levels in cooked vegetables were increased by spiking with hexoses. However, in pumpkin puree, only about 20% of furan was formed from sugars, preferably from the intact carbon skeleton.  相似文献   

4.
Only a minor part of Maillard reaction studies in the literature focused on the reaction between carbohydrates and peptides. Therefore, in continuation of a previous study in which the influence of the peptide C-terminal amino acid was investigated, this study focused on the influence of the peptide N-terminal amino acid on the production of pyrazines in model reactions of glucose, methylglyoxal, or glyoxal. Nine different dipeptides and three tripeptides were selected. It was shown that the structure of the N-terminal amino acid is determinative for the overall pyrazine production. Especially, the production of 2,5(6)-dimethylpyrazine and trimethylpyrazine was low in the case of proline, valine, or leucine at the N-terminus, whereas it was very high for glycine, alanine, or serine. In contrast to the alkyl-substituted pyrazines, unsubstituted pyrazine was always produced more in the case of experiments with free amino acids. It is clear that different mechanisms must be responsible for this observation. This study clearly illustrates the capability of peptides to produce flavor compounds such as pyrazines.  相似文献   

5.
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.  相似文献   

6.
The effects of five ginsenosides (G-Rh2, -Rd, -Rb1, -Rb2, -Rh1) isolated from the root of Panax gingseng on stimulus-induced superoxide generation in human neutrophils were evaluated by measuring the reduction of ferricytochrome c. The tyrosyl or serine/threonine phosphorylation of neutrophil proteins and translocation of p47phox, p67phox, and Rac to the plasma membrane were detected using specific monoclonal antibodies. G-Rh2 significantly suppressed superoxide generation induced by N-formylmethionyl-leucylphenylalanine (fMLP), phorbol 12-myristate 13-acetate (PMA), and arachidonic acid (AA) in a concentration-dependent manner. G-Rh1 showed a comparably lower suppression on fMLP-induced superoxide generation. G-Rd, -Rb1, and -Rb2 also suppressed AA-induced superoxide generation in high concentrations. G-Rd and G-Rb1 showed no effect on fMLP- and PMA-induced superoxide generation. FMLP-, PMA-, and AA-induced tyrosyl or serine/threonine phosphorylation and translocation of p47phox, p67phox, and Rac to the plasma membrane were in parallel with the suppression of the stimulus-induced superoxide generation.  相似文献   

7.
Alkylpyrazines are a very important class of Maillard flavor compounds, but their mechanism of formation is complex and consists of different pathways. The model reaction of 20 different amino acids with 1,3-dihydroxyacetone, as a precursor of 2-oxopropanal, was studied by means of SPME-GC-MS to investigate the involvement of the amino acid side chain in the substitution pattern of the resulting pyrazines. 2,5-Dimethylpyrazine was quantitatively the most important pyrazine formed from all of the amino acids. The amino acid side chain is not involved in its formation. The substituents of other less abundant pyrazines resulted mainly from the incorporation of the Strecker aldehyde or aldol condensation products in the intermediate dihydropyrazine. The importance of different reaction mechanisms was evaluated, taking into account the pattern of pyrazines identified. In the solvent extracts of aqueous model reactions of 2-oxopropanal with amino acids, the main reaction product was not a pyrazine but a novel pyrrole. This pyrrole was identified as 2,5-diacetyl-3-methyl-1 H-pyrrole by means of spectral analysis, secured by chemical synthesis. A reaction mechanism for its formation was proposed and evaluated. The influence of various reaction conditions on the formation of 2,5-diacetyl-3-methyl-1 H-pyrrole and 2,5-dimethylpyrazine in the model reaction of alanine with 2-oxopropanal was studied. These results underscore the importance of the ratio of the different reagents and the presence of water in the resulting flavor formation in the Maillard reaction.  相似文献   

8.
Thermal degradation studies of food melanoidins   总被引:1,自引:0,他引:1  
Food melanoidins were isolated from bread crust, coffee, and tomato sauce and their composition was investigated by thermal degradation. Among the generated volatiles, important food flavor compounds were detected: in particular furans, carbonyl compounds, 1,3-dioxolanes, pyrroles, pyrazines, pyridines, thiophenes, and phenols. The results indicated that the isolated melanoidin fractions mainly consisted of compounds formed from carbohydrates and their degradation products. Besides proteins, other food constituents were incorporated in the melanoidin structure as well, such as lipid oxidation products in tomato melanoidins and phenolic compounds in coffee melanoidins. A comparison of the thermal generation of volatiles between these food-derived melanoidins and model melanoidins prepared from a single carbonyl compound and an amino acid showed that the degradation pattern of food melanoidins is quite different from that obtained from a glucose-glycine model system.  相似文献   

9.
The free amino acid profile of 18 samples of tronchuda cabbage ( Brassica oleracea L. var. costata DC) leaves, harvested at three different months, was determined by HPLC/UV-vis. The tronchuda cabbage leaves total free amino acid content varied from 3.3 to 14.4 g/kg fresh weight. Generally, arginine was the major compound, followed by proline, threonine, glutamine, cysteine, and glutamic acid. This study indicates that free amino acids are not similarly distributed: in external leaves, proline and arginine were the major free amino acids, while in internal ones, arginine was the main free amino acid, followed by threonine, glutamine, and cysteine. Significant differences were observed for valine, proline, arginine, leucine, cysteine, lysine, histidine, and tyrosine contents. The levels of some free amino acids were significantly affected by the collection period. In external leaves, this occurred with glutamic acid, serine, valine, leucine, cysteine, and ornithine contents, while in internal leaves, it occurred with aspartic acid, arginine, and total contents.  相似文献   

10.
The effect of different sugars and glyoxal on the formation of acrylamide in low-moisture starch-based model systems was studied, and kinetic data were obtained. Glucose was more effective than fructose, tagatose, or maltose in acrylamide formation, whereas the importance of glyoxal as a key sugar fragmentation intermediate was confirmed. Glyoxal formation was greater in model systems containing asparagine and glucose rather than fructose. A solid phase microextraction GC-MS method was employed to determine quantitatively the formation of pyrazines in model reaction systems. Substituted pyrazine formation was more evident in model systems containing fructose; however, the unsubstituted homologue, which was the only pyrazine identified in the headspace of glyoxal-asparagine systems, was formed at higher yields when aldoses were used as the reducing sugar. Highly significant correlations were obtained for the relationship between pyrazine and acrylamide formation. The importance of the tautomerization of the asparagine-carbonyl decarboxylated Schiff base in the relative yields of pyrazines and acrylamide is discussed.  相似文献   

11.
蚕豆根系分泌物中氨基酸含量与枯萎病的关系   总被引:5,自引:0,他引:5  
通过田间试验研究不同品种蚕豆枯萎病病情指数的差异,并通过水培试验鉴定蚕豆根系分泌物中氨基酸组分并测定氨基酸的含量,分析各氨基酸组分与蚕豆枯萎病病情指数的相关性。结果表明:根系分泌物中氨基酸总量随着蚕豆枯萎病抗性的降低而升高。感病品种和中抗品种中检出15种氨基酸,而抗病品种中检出14种,组氨酸只存在于中抗品种中,脯氨酸仅在感病品种中检测到,3个蚕豆品种根系分泌物中均未检出精氨酸。丝氨酸(Ser)、蛋氨酸(Met)和赖氨酸(Lys)与枯萎病病指呈负相关关系,以Ser的相关系数最高,其他13种氨基酸含量与蚕豆枯萎病的病情指数呈正相关。蚕豆根系分泌物中Ser、Met和Lys含量及Ser/Gly、Ser/Ala比值高能抑制枯萎病的发生与发展,而天门冬氨酸(Asp)、苏氨酸(Thr)、甘氨酸(Gly)、丙氨酸(Ala)、缬氨酸(Val)、酪氨酸(Tyr)、苯丙氨酸(Phe)含量高时能促进枯萎病的发生。不同蚕豆品种根系分泌的氨基酸含量与组分的差异是影响蚕豆对枯萎病抗性差异的重要原因之一。  相似文献   

12.
玉米浆发酵产生物丁醇的氨基酸代谢动力学模拟   总被引:1,自引:0,他引:1  
为了深入挖掘利用丙酮丁醇梭菌产生物丁醇过程中氨基酸代谢的动态过程,探究利用廉价氮源玉米浆中的氨基酸用于丙酮丁醇梭菌产生物丁醇的生产策略,寻找生产丁醇的高效率廉价氮源来降低发酵生产成本。该研究首先利用高通量测序技术对玉米浆中微生物多样性进行分析;同时基于丙酮丁醇梭菌(Clostridium acetobutylicum)生产丙酮-丁醇-乙醇(Acetone-Butanol-Ethanol,ABE)碳代谢动态模型的基础上,构建氨基酸代谢模型,以此模拟15种氨基酸在利用木糖为碳源发酵生产ABE中的氨基酸代谢过程,并对氨基酸的代谢与丙酮丁醇梭菌的生物量以及ABE的合成相关性关系进行冗余分析;通过模型预测实际生产中利用玉米浆发酵时氨基酸的消耗过程。结果表明,梭状芽胞杆菌属(Clostridium)占细菌总数的68.76%,是玉米浆中的优势菌群;最佳参数校正后构建了氨基酸代谢模型,模拟值与试验值有较好拟合度;11种氨基酸(苯丙氨酸、苏氨酸、异亮氨酸、亮氨酸、蛋氨酸、缬氨酸、酪氨酸、甘氨酸、丝氨酸、精氨酸、天冬酰胺)在培养过程中迅速消耗用于细胞生长和溶剂生成,3种氨基酸(脯氨酸、组织胺、天冬氨酸)保持稳定状态,同时发酵过程中谷氨酰胺积累;冗余分析表明其中5种氨基酸对发酵产物及生物量影响具有相关性(P<0.05),相关性排序从大到小依次为丝氨酸、甘氨酸、亮氨酸、缬氨酸、天冬酰胺;模拟预测玉米浆中缬氨酸、甘氨酸、丝氨酸在发酵过程中基本被消耗,推测其为发酵后期的营养限制性因子。该结论可证实玉米浆可作为丙酮丁醇梭菌发酵丁醇的优势氮源,为丙酮丁醇梭菌的氨基酸代谢调控及下一步利用并优化玉米浆作为氮源生产生物丁醇提供一定的理论参考和数据支撑。  相似文献   

13.
Furan has recently received attention as a possibly hazardous compound occurring in certain thermally processed foods. Previous model studies have revealed three main precursor systems producing furan upon thermal treatment, i.e., ascorbic acid, Maillard precursors, and polyunsaturated lipids. We employed proton transfer reaction mass spectrometry (PTR-MS) as an on-line monitoring technique to study furan formation. Unambiguous identification and quantitation in the headspace was achieved by PTR-MS/gas chromatography-mass spectrometry coupling. Ascorbic acid showed the highest potential to generate furan, followed by glyceryl trilinolenate. Some of the reaction samples generated methylfuran as well, such as Maillard systems containing alanine and threonine as well as lipids based on linolenic acid. The furan yields from ascorbic acid were lowered in an oxygen-free atmosphere (30%) or in the presence of reducing agents (e.g., sulfite, 60%), indicating the important role of oxidation steps in the furan formation pathway. Furthermore, already simple binary mixtures of ascorbic acid and amino acids, sugars, or lipids reduced furan by 50-95%. These data suggest that more complex reaction systems result in much lower furan amounts as compared to the individual precursors, most likely due to competing reaction pathways.  相似文献   

14.
The chemical reactivity of 5-(hydroxymethyl)-2-furaldehyde (HMF) with lysine, glycine, and proline was studied using isotope labeling technique. To confirm the formation of HMF adducts in glucose amino acid model systems, a useful strategy was developed in which products simultaneously possessing six glucose (HMF moiety) and any number of amino acid carbon atoms in addition to nitrogen were targeted using specifically labeled precursors such as [(15)N(α)]lysine·2HCl, [(15)N(ε)]lysine·2HCl, [U-(13)C(6)]lysine·2HCl, [(13)C(6)]lysine·2HCl, and [U-(13)C(6)]glucose in the case of lysine model system. In addition, model systems containing HMF and amino acids were also studied to confirm specific adduct formation. Complete labeling studies along with structural analysis using appropriate synthetic precursors such as HMF Schiff base adducts of piperidine and glycine have indicated that HMF generated in the glucose/amino acid model systems initially forms a Schiff base adduct that can undergo decarboxylation through an oxazolidin-5-one intermediate and form two isomeric decarboxylated Schiff bases. Unlike the Schiff bases resulting from primary amines or amino acids such as glycine or lysine, those resulting from secondary amino acids such as proline or secondary amines such as piperidine can further undergo vinylogous Amadori rearrangement, forming N-substituted 5-(aminomethyl)furan-2-carbaldehyde derivatives.  相似文献   

15.
The changes in amino acid composition that occur with maturity of the Noble cultivar of the Vitis rotundifolia Michx. (muscadine) grape were determined by HPLC. Eighteen amino acids were identified. Histidine was the most prominent amino acid followed by alanine. The concentrations of most of the major amino acids (alanine, glycine, histidine, valine, isoleucine, aspartic acid, and serine) were highest at verasion. Glutamine and threonine contents dropped sharply after fruit set, while those of arginine and proline increased gradually with maturity and ripening. Tyrosine content increased gradually with maturity and ripening following a slight drop after fruit set. In ripe grapes, seeds contained most of the amino acids in mature grapes (50%) followed by the pulp (23%), the juice (15%), and the skin (11%). Alanine, histidine, and arginine were the principal amino acids identified in the juice. Alanine, histidine, arginine, valine, glutamine, aspartic acid, proline, serine, and threonine accounted for about 90% of the amino acids in the pulp. In seeds, alanine, proline, asparagine, and histidine accounted for over 55% of the amino acids, while alanine and histidine were found to be the predominant free amino acids in the skin. The profile indicates some differences in the changes in amino acid composition with berry maturity and relative amounts of amino acids present in muscadine compared to those in nonmuscadine grape species.  相似文献   

16.
Summary Organic matter was extracted from three soils, a cultivated Berwick sandy loam, a cultivated Franklin loamy sand, and an uncultivated Cumberland silty loam. Gel-permeation chromatography was used to separate organic matter extracts into high- (HMW) and low-molecular-weight (LMW) fractions. Reversed-phase high performance liquid chromatography was used to separate and collect the LMW peptide fractions. Peptide samples were hydrolyzed with immobilized proteases attached to beaded agarose and carboxymethyl cellulose in column and batch reaction systems. The chromatograms suggested that peptides are bound to common soil components. The amino acids released in the greatest percentages were relatively non-polar. Large percentages of serine, glycine, alanine, threonine, and valine were observed in the LMW soil peptides. Little aspartic acid, asparagine, glutamic acid, glutamine, arginine, and no histidine was detected in the LMW soil peptides. The soil peptides released different amino acid percentages and quantities when hydrolyzed by immobilized proteases attached to different supports. The quanitities of amino acids released by batch hydrolysis differed from those obtained with column hydrolysis. Greater quantities of amino acids were released (by both types of immobilized protease) from the LMW peptide hydrolysates of the two cultivated soils than from the uncultivated soil.  相似文献   

17.
18.
Extraction of a copper contaminated soil material by the percolation of an amino acid containing residue hydrolysate. 2. Time course of amino acid elution and input/output balance of amino acids During 16 days an amino acid containing blood meal hydrolysate (amino acid concentration: 188 mMol·L?1) was percolated through a column packed soil material (soil content per column: 4.1 kg dry weight, four parallels). The copper contaminated material (soil type: Typic Udifluvent, soil texture: sandy loam, loamy sand) was sampled from an area formerly used for cultivation of hop (Humulus lupus). Besides the investigation of the copper liberation the experiments aimed to determine the elution dynamic and input/output balance of amino acids (time span for amino acids balance 14 days). In total 11.7 L of hydrolysate, containing 2.2 Mol of amino acids, were introduced into each column. The mean amino acid output with the column effluent was 1.13 Mol. This corresponds to an elution degree of 51.2%, related to the sum of applicated amino acids, and to a mean substance specific elution degree of 48.4% reflecting the elution of 15 compounds. The substance specific elution ranged from 9.6% (serine) to 75.5% (valine). The highest concentrations of serine and threonine were determined in the effluents after two days, whereas the histidine concentration was highest at the last sampling. The differences in the percolation properties of the amino acids are discussed in terms of important retention and elimination processes (biodegradation, ad-/desorption, intercalation).  相似文献   

19.
Duck eggs were pickled in 4.2% NaOH/5% NaCl solution for 20 days to prepare the traditional Chinese Pidan. The extent of racemization of compositional amino acid in egg albumen and yolk over the alkaline pickling period was investigated with micellar capillary electrophoresis (MCE) using beta-cyclodextrin as chiral selector. The racemization value of amino acids in egg albumen was in the order serine > aspartic acid > glutamic acid > phenylalanine > leucine > valine > threonine = isoleucine, whereas the order in egg yolk was aspartic acid > glutamic acid > phenylalanine > leucine > valine. Therefore, the tendency of amino acid racemization appeared to be closely related to the properties of its residual side chain, as well as the pH and alkaline treating period. Moreover, racemization of most of the amino acids was remarkably induced by the alkaline treatment during the initial pickling period.  相似文献   

20.
The qualitative and quantitative composition of free amino acids in a typical Finnish peat bog at various depths down to 5.3 m below the surface was studied using capillary gas chromatography and mass spectrometry. Sixteen amino acids were identified at each depth: α-alanine, β-alanine, glycine, valine, leucine, proline, isoleucine, serine, threonine, glutamic acid, aspartic acid, phenylalanine, tyrosine, γ-aminobutyric acid, ornithine and lysine. Their amounts decreased markedly at a depth of 40–100 cm. The total amount of amino acids varied between 0.6 and 5.6 g kg?1 dry matter (i.e. 0.06–0.56%) depending on the depth. The proportion of neutral amino acids was greatest at all depths studied, except at the surface layer where it ranged between 41 and 72% by mass. The acidic amino acids decreased with depth from 56 to 23% of the total. The proportion of aromatic amino acids was very small, 3.2–5.5% by mass. In samples from aerobic conditions, where the microbial production of free amino acids was the greatest, α-ala, gly, glu and asp were most abundant. In peat from anaerobic conditions, where the microbiological activity was low, the proportion of the most chemically stable amino acid was exceptionally high. This may have been because glycine was a degradation product of other amino acids or peptides. Peat type and degree of decomposition had a strong influence on the total amount of free amino acids and their qualitative composition.  相似文献   

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