The Thiobarbituric Acid (TBA) Reaction in Foods: A Review

The wide diffusion of 2-thiobarbituric acid (TBA) in the scientific literature is due to the TBA assay, or TBA test, which has been employed in the determination of autoxidative alterations of fats and oils. Two processes occur in autoxidation, generally: the free radical and the photo-oxidation mechanisms. The better studied is the free radical mechanism. The hydroperoxiepidioxides and bicycloendoperoxides are malonaldehyde (MDA) precursors. The absorption spectrum obtained with oxidized fatty foods is like the spectrum obtained when TBA and MDA react. However, during the secondary phase of the autoxidation process other aldehydes (alkanals, 2-alkenals, dienals) are formed which react with TBA, and they are responsible for off-flavors. Three kinds of pigments (yellow, orange, red adducts) are involved. Also, aromatic aldehydes, which constitute the flavor profile of diverse fruits and essential oils, form with TBA the characteristic arylidene-2-TBA acids. Other substances, such as ketones, ketosteroids, acids, esters, sugars, imides and amides, amino acids, oxidized proteins, pyridines, pyrimidines, and vitamins can react with TBA; they are named TBARS (substances that react with TBA), and form principally in meats and meat derivatives. Several organic or bio-organic acids, as shikimic and sorbic acids, react photometrically with TBA if a Malaprade reaction takes place before. A structural study of the red adduct TBA-MDA has been carried out.     

7种氨基酸与丙烯醛典型反应产物的表征

为探究油炸薯片中的内源有害物丙烯醛产生后显著消减的原因,本研究利用马铃薯中7种含量较高的氨基酸(甘氨酸、天冬酰胺、天冬氨酸、谷氨酸、谷氨酰胺、缬氨酸、苏氨酸)与丙烯醛在不同温度及时间条件下反应,对反应产物进行分离纯化和结构鉴定,研究氨基酸对丙烯醛的清除作用及其作用机理.研究发现,所选氨基酸可高效消除丙烯醛,并生成8种首...     

MEASUREMENT OF THE RELATIVE TASTE INTENSITY OF SOME L-α-AMINO ACIDS AND 5'-NUCLEOTIDES

SUMMARY— Intensity of glutamate-like and/or inosinate-like taste (umami in Japanese) of various flavor amino acids and flavor nucleotides was studied using sensory analysis and always found proportional to that of monosodium glutamate (MSG) and disodium 5'-inosinate (IMP), respectively. By application of this fact to a previously obtained equation expressing the relationship between the taste intensity of MSG-IMP mixture and that of MSG alone, the intensity of umami of the mixture of any flavor amino acids and nucleotides could be expressed as an elementary equation: y = u +γ uv, where u and v are the concentrations of amino acids and nucleotides in terms of the concentrations of MSG and IMP, respectively, in the mixture; y is the equivalent concentration of MSG alone; and γ is a positive constant. Interrelationships within each group of substances were additive.     

聚氨酯改性胶原蛋白的机理及应用研究(1)一氨基酸与甲苯二异氰酸酯的反应

选取具有不同侧链基团的氨基酸和甲苯二异氰酸酯,在催化剂存在的条件下进行液固反应,观察反应情况,用红外光谱对反应物进行表征。通过红外谱图及理论分析讨论得出,氨基酸中活性基团和甲苯二异氰酸酯中异氰酸酯基团的反应顺序,为聚氨酯改性胶原蛋白提供一定的理论依据。     

Cyclocondensation of 2,3-butanedione in the presence of amino acids and formation of 4,5-dimethyl-1,2-phenylendiamine

The chemical interaction of 2,3-butanedione with amino acids through Strecker reaction has been studied extensively. However, the formation of previously reported 4,5-dimethyl-1,2-benzoquinone from 2,3-butanedione/amino acid model systems has not been investigated in detail. In this study such model systems containing 2,3-butanedione were investigated under pyrolytic conditions using glycine, sodium glycinate and glycine hydrochloride as amino acids able to modulate acid/base catalytic activity of the reaction medium. The analysis of the data indicated that replacing glycine with its corresponding salts promoted significantly the generation of 2,3,6,7-tetramethylquinoxaline relative to tetramethylpyrazine, the indicator compound for the Strecker reaction. The origin of the 2,3,6,7-tetramethylquinoxaline was traced back to the formation of 4,5-dimethyl-1,2-benzoquinone through isotope labelling studies. Furthermore, these studies have also indicated the ability of glycine not only to catalyse the cyclocondensation of butanedione into 4,5-dimethyl-1,2-benzoquinone but also its conversion into 4,5-dimethyl-1,2-phenylenediamine through Strecker-type transformations. The trapping of 2,3-butanedione by this in situ generated 4,5-dimethyl-1,2-phenylenediamine gave rise to the observed 2,3,6,7-tetramethylquinoxaline.     

Reactivity of acrylamide with coffee melanoidins in model systems

Coffee and its substitutes have been described as complex matrices for acrylamide (ACR) analysis due to both analytical interferences and ACR instability in the matrix. Melanoidins are multifunctional and biochemically active polymers which are formed in large extent during coffee roasting. Model systems composed of ACR (elimination studies) or glucose-asparagine (ACR formation/elimination studies) with/without melanoidins was heated at 180 °C. Washed sea sand and cellulose microcrystalline were used as matrix. Coffee melanoidins had a direct influence on the fate of ACR under heating, while the effect was not observed at room temperature. In addition, ACR decrease was also related to the reaction time and the initial amount of melanoidins in the media, where clearly a dose-response was observed. In contrast, pH (from 3.5 to 7.0) had no significant effect on ACR reactivity towards melanoidins. It is hypothesized that nucleophilic amino groups of amino acids from the proteinaceous backbone of melanoidins react via the Michael addition reaction with ACR, although the exact mechanism is unknown. Then, melanoidins could modulate the reaction pathways of ACR formation and elimination during coffee roasting and serve as acrylamide-mitigation substance.     

Nonvolatile taste compounds in cooked Chinese Nanjing duck meat following postproduction heat treatment

Abstract: Taste‐active compounds, including free amino acids, succinic acid and 5′‐nucleotides, and chemical components including moisture, pH, protein, crude fat, and sodium chloride were evaluated in cooked and packaged Chinese Nanjing ducks following heat treatments including control, 99 °C for 40 min, 108 °C for 20 min, 92 °C microwave followed by water heating, 95 °C for 30 min, 121 °C for 25 min. Heat treatment decreased (P < 0.05) the content of Alamine and moisture and reduced the pH value in muscle, but increased (P < 0.05) the protein and 5′‐nucleotides content. The 99 °C group had a significantly lower crude fat content compared with other groups (P < 0.05). The succinic acid content in the control group was significantly higher than in the 121 °C group (P < 0.05). Groups treated at higher temperatures (108 °C, 121 °C, and microwave) had similar equivalent umami concentrations and 5′‐nucleotides, free amino acids content, as well as the derived bitter and sweet taste components compared with the groups treated at lower temperatures. It can be speculated that these differences account for the enhanced flavor of the meat in the 99 °C, 108 °C, 121 °C, and microwave groups compared with the untreated control. Therefore, heat treatment at lower temperature after packaging may prolong product shelf life without any detrimental effects on taste. The results of this study indicate that it is important to use lower temperatures in this type of food processing. However, it may be possible to modify the primary processing steps to improve the content of umami‐like taste compounds such as 5′‐nucleotides. Practical Application: Heat treatment of packaged products is an effective method for eradication of microbes, therefore increasing the shelf‐life. However, such treatment can result in major changes in the sensory perception of meat products, particularly the formation of off‐flavors. This study investigated changes in taste‐active compounds in duck meat following a number of types of heat treatment.     

沙蚕不同蛋白酶酶解产物滋味特征及聚类分析研究

摘要：目的 研究沙蚕不同酶解产物中氨基酸和呈味核苷酸的含量、组成和呈味效果差异。方法 以酱油粉为对照,采用味道强度值、味精当量、主成分分析法、聚类分析法进行分析和综合评价。结果 沙蚕不同蛋白酶解产物中游离氨基酸含量在90.84±1.12~151.25±0.95 mg/g之间;风味蛋白酶酶解产物的游离氨基酸和呈味氨基酸含量最高;胰蛋白酶组的味精当量值远高于酱油粉组;各组氨基酸对滋味有较大贡献,风味、胰蛋白酶组中谷氨酸的味道强度值值与酱油粉组中该值接近,分别为37.13和35.40 mg/g。提取了4个主成分,累计方差贡献率达95.372%,较好地反应了酶解产物中游离氨基酸的综合信息,风味蛋白酶组综合得分最高,基于电子舌的滋味轮廓也支撑了这一结论。采用聚类分析将实验组分为4类,较直观地反映了不同酶解产物间的差异。结论 风味蛋白酶和胰蛋白酶酶解沙蚕的产物游离氨基酸品质较好,且鲜味氨基酸含量和呈味核苷酸含量较高,可开发呈味基料。     

不同杀菌处理对秋刀鱼软罐头营养及滋味的影响

本文评估了橄榄油油浸结合超高压杀菌应用于秋刀鱼软罐头加工的潜力,设置了五种处理方式:不加橄榄油的未杀菌组、橄榄油油浸的超高压杀菌（UHPSO）组、不加橄榄油的超高压杀菌（UHPS）组、橄榄油油浸的传统热杀菌(RSO)组以及不加橄榄油的传统热杀菌（RS）组,并对不同处理组秋刀鱼软罐头营养（基本营养成分、氨基酸和脂肪酸）及滋味（游离氨基酸和呈味核苷酸）的相关指标进行对比分析。结果表明:UHPSO组的粗脂肪、粗蛋白含量高于其他杀菌处理组,营养价值更高;不同杀菌处理的秋刀鱼软罐头氨基酸组成均符合FAO/WHO推荐模式且不存在限制性氨基酸,UHPSO组氨基酸评分最高,尤其是补充含硫氨基酸及赖氨酸的优质来源;与传统热杀菌相比,超高压杀菌可以更好抑制不饱和脂肪酸的氧化降解,结合橄榄油油浸处理的秋刀鱼软罐头是补充n-3多不饱和脂肪酸的优质来源。与未杀菌组相比,4种杀菌处理均导致游离氨基酸和呈味核苷酸含量增加,结合滋味活性值和味精当量值,发现谷氨酸、苏氨酸、天冬氨酸、丙氨酸和次黄嘌呤对秋刀鱼软罐头鲜美滋味的形成具有重要的贡献作用,其中UHPSO组鲜味最强。综合分析,与传统热杀菌相比,橄榄油油浸结合超高压杀菌处理的秋刀鱼软罐头营养丰富,滋味更加鲜美。     

Cross-linking of tyrosine-containing peptides by hydrogen peroxide-activated <Emphasis Type="Italic">Coprinus Cinereus</Emphasis> peroxidase

Hydrogen peroxide-activated Coprinus Cinereus peroxidase (CIP) can initiate polymerization of tyrosine-containing peptides via initial formation of an intermediate tyrosyl radical, which for the first time has been identified by spin trap electron spin resonance spectroscopy as located on carbon 1 in the aromatic ring, and subsequent formation of either dityrosine or isodityrosine bonds through a net elimination of two hydrogen atoms between peptides. The rate and degree of polymerization were found to depend on peptide size and the amino acid adjacent to tyrosine, as longer peptides and amino acids with bulky side groups were less reactive. In the forwarded hypothesis for the reaction mechanism upon peroxidase-initiated cross-linking of tyrosine-containing peptides and proteins, it is suggested that the polymerization takes place through a radical chain reaction. The polymerization reaction shows the potential of CIP as a protein structure-engineering tool to control functionality of proteinious food matrices or in biopolymer formation.     

On the Adequacy of Methods for the Quantitative Determination of Reactive Lysine in the Free Form or in Small Peptides

Reactive lysine determination in mixtures containing lysine in the free form or in small peptides by the l-fluoro-2,4-dinitrobenzene (FDNB) procedure is complicated by the fact that both amino groups of lysine can react with FDNB. Quantitative conversion of lysine to its copper salt, followed by reaction with FDNB, has been reported. However, the present study demonstrated that copper complexation was incomplete, even when alanine was added to better protect the free α-amino group of lysine. The FDNB procedure would, therefore, be of questionable value for the determination of reactive lysine in protein hydrolysates.     

Nonenzyme browning and its effect on protein nutrition

The nonenzyme browning involves the thermal decomposition of sugars, the caramelization, the decomposition of oxi‐acids, the so called “Maillard reaction” between amino acids and carbohydrates, the reaction between oxidized fats and proteins, and those alterations which take place by the alkaline treatment of proteins. The Maillard reaction is of secondary importance in the case of foodstuffs and fodders with low carbohydrate contents (meats, meat meal, fish meal). By the heat treatment, the sulphur‐containing amino acids of proteins (cystine, methionine) are damaged primarily because of oxidation, but the decrease in the amount of threonine, serine, tryptophan, and lysine is observable too. According to the formation of enzyme resistant cross‐links, the in vitro and in vivo digestibility of protein decreases after the heat treatment and the communication with oxidized fats. Besides the amino acids mentioned, the possibility of enzymatic break‐off of leucine and isoleucine is reduced too. In the course of the heating of proteins the occurance of racemization has to be considered too (formation of alloisoleucine). The basic mechanism of the reaction between sugars and simple amino acids is already essentially explained: amino‐acids break off after the formation glycosilamines and Amadori products but they are linked irreversibly to some, partly unsaturated decomposition products of sugars, types of 6 and 3 carbon atoms. The decrease in the biological usability of amino acids starts already with the Amadori products. The reactivity of the single amino acids depends on the number of carbon atoms, on the basicity, and on the polarity of the amino acid molecule. The especially highly reactive amino acids of proteins are (1) the essential lysine (because of its 6‐NH₂ group), (2) other types of basic amino acids, and (3) tryptophan (because of the lability of the indole ring), methionine, cystine and threonine. In the Maillard reaction of tryptophan the —NH— group of the indole ring is involved too. The Maillard reaction is highly influenced by the pH of foodstuffs or other agents. The reduction of pH which may be performed by the increase of fermentation in the baking industry, lessens the decomposition of lysine and tryptophan in proteins. The raise of pH in basic domain enhances the Maillard reaction up to a maximal value but a decrease may be observed when the pH is raised further on. In foodstuffs and in other solid protein‐carbohydrate systems the increase of the moisture content generally enhances the Maillard reaction, the sensibility of the single amino acids to the changes in the moisture content is different. In the case of the alkaline treatment of proteins, we must reckon not only with the decomposition of single amino acids, first of all that of cystine by beta‐elimination, but with the formation of some amino acid derivatives as lysinoalanine, lanthionine, and in ornithinoalanine too. Presently lysinoalanine is of toxicological importance as proved by experiences on rats. The isomerization of essential amino acids may appear too during the alkaline treatment of proteins and this bears a reducing effect on the nutritive’ value.     

氨基酸对葡萄糖-天冬酰胺模拟体系中丙烯酰胺形成的抑制作用研究

目的 研究4种氨基酸对已建立的葡萄糖-天冬酰胺模拟体系中丙烯酰胺生成的影响。方法 以葡萄糖-天冬酰胺组为对照组,在此基础上分别加入半胱氨酸、甘氨酸、赖氨酸和谷氨酸4种氨基酸为实验组,于140℃反应5～30min,测定反应后模拟体系的褐变程度、色差值、生成丙烯酰胺含量和剩余葡萄糖含量。结果 4种氨基酸中,半胱氨酸和谷氨酸对模拟体系中的褐变度和色差值的抑制作用较好;半胱氨酸和赖氨酸对底物葡萄糖的消耗作用较快;半胱氨酸对丙烯酰胺的抑制效果最好,抑制率为(76.00±0.73)%,其他氨基酸的抑制率分别为甘氨酸(38.39±0.44)%、赖氨酸(51.03±3.09)%和谷氨酸(28.76±2.43)%;进一步研究发现,当添加4.2mmol半胱氨酸时,丙烯酰胺抑制率达(95.32±0.47)%。结论 4种氨基酸相比,半胱氨酸对丙烯酰胺形成的抑制效果最好,且对于降低葡萄糖-天冬酰胺模拟体系的褐变度、色差值、葡萄糖含量有较好的效果。     

酵母自溶过程中的氨基酸溢出动力学

对不同自溶程度的干酵母细胞蛋白降解溢出的氨基酸摩尔组份(MF)进行了测定。结果表明,丙氨酸、赖氨酸和谷氨酸在自溶液中占有优势的MF值,高达41％。各种氨基酸的溢出速度变化与其分子结构特点,特别是R基的极性关系密切。氨基酸的溢出动力学方程基本可归纳为直线型、对数型和偏态钟型3组。在β—转角出现频率高和氨基酸种类的溢出初速度相对较大,含有非极性R基的氨基酸的溢出延滞期则相对较长。添加蛋白酶可促进在β—转角肽段中出现频率高的氨基酸的水解,增加鲜味和甜味氨基酸的MF值,减少苦味氨基酸的MF值,但有5种必需氨基酸的MF值也显著下降。浓缩处理使自溶液中的氨基酸含量减少,半胱氨酸和苏氨酸的MF值分别减少33％和25％。     

鲜味料的作用机理及汤精在烹调中的应用

文中论述了鲜味氨基酸、鲜味核苷酸的的作用机理，分析了味精、鸡精和汤精的区别，并阐述了汤精的特点和质量标准及其在菜肴传统烹制技法中的应用。     

不同生长阶段下中华绒螯蟹滋味成分差异研究

本文比较了8月份到12月份下中华绒螯蟹雄蟹滋味物质间的差异。通过用电子舌区分不同月份下中华绒螯蟹三个可食部位(体肉、性腺、肝胰腺)的滋味轮廓,并测定其游离氨基酸和呈味核苷酸含量,计算TAV值、EUC值,结果表明电子舌能较好区分不同月份下各可食部位滋味轮廓间的差异,11月份、12月份的滋味轮廓与8月份、9月份相比差异较大;三个可食部位中呈甜味氨基酸含量与性腺中呈鲜味氨基酸含量均在11月份达到最高;蟹肉中呈味核苷酸总量最高,且波动较大,11月份以后呈鲜味核苷酸和呈甜味核苷酸含量显著增高,而性腺和肝胰腺中呈味核苷酸含量波动较小;不同阶段下中华绒螯蟹各可食部位的Glu、Ala、Arg和Lys的TAV值均大于1,对蟹的整体滋味贡献较大;性腺中的EUC值显著高于其他部位,并且在9月份、12月份达到最高。综上,雄蟹在11月份滋味最佳。     

Cloning and sequencing the genomic encoding region of copper-zinc superoxide dismutase enzyme from several marine strains of the genus Debaryomyces (Lodder & Kreger-van Rij)

Copper-zinc superoxide dismutase (SODC) is a cytosolic enzyme which catalyses the dismutation of the superoxide radical. Due to its physiological importance, the encoding genes have been cloned from several species of higher eukaryotes. However, genes from moulds and yeast have not been studied extensively. In this paper, the encoding region of this gene (sod1) has been cloned from several strains of marine yeast belonging to the genus Debaryomyces (dvv sod1, dvy sod1 and dh sod1-61) through genomic DNA-PCR amplification. Fragments of 480-486 nucleotides were obtained, which contain information for products of 153-156 amino acids with calculated molecular masses of 15.8-16.6 kDa. The deduced amino acid sequence shows that D. vanrijiae enzymes present three additional amino acids not closely related to the active site conformation. In addition, in D. vanrijiae var. vanrijiae (strain 020), one histidine residue is apparently replaced by a proline; the incidence and function of other aromatic or heterocyclic amino acids is discussed. Homology and phylogenetic trees were constructed from amino-acid sequence multi-alignment analyses; the interrelationships among fungi are discussed. The sod-1 sequences reported in this paper were deposited in the public data library of the NCBI under Accession Nos AF301019, AF327449 and AF327448.     

饲喂干酪乳杆菌K17对加州鲈鱼肌肉滋味的影响

为改善饲喂加州鲈鱼肌肉的滋味，研究了添加干酪乳杆菌K17的饲料对加州鲈鱼肌肉滋味物质的影响。试验分为6组:含1×108CFU/g干酪乳杆菌K17的饲料组（LB），含10％脱脂乳粉保护的1×108CFU/g干酪乳杆菌K17的饲料组（MB），含1×108CFU/g热灭活干酪乳杆菌K17的饲料组（DB），含发酵上清液的饲料组（FS）、含10％脱脂乳粉的饲料组（MG）及含0.85％生理盐水的饲料组（SG）。实验结束后，利用电子舌测定了不同处理组样本的整体滋味差异，并分析了其呈味氨基酸和呈味核苷酸的含量。结果显示，通过电子舌主成分分析和判别因子分析，可将6组的差异性进行有效区分；采用雷达图能将各组鲜味、苦味和甜味大小区分。6组加州鲈鱼肌肉中检测出16种游离氨基酸。MB组鲜味氨基酸总量和天冬氨酸含量，FS组缬氨酸、异亮氨酸、亮氨酸、苯丙氨酸含量和苦味氨基酸总量和MG组的必需氨基酸总量显著高于对照组SG（P<0.05）。MB组的味精当量（Equivalent umami concentrations，EUC）增加最明显，与对照组相比差异显著（P<0.05），6组EUC的大小为MB>FS>DB>LB>MG>SG，与电子舌预测结果基本一致。以上研究表明，饲喂不同剂型干酪乳杆菌K17对加州鲈鱼滋味成分和含量的影响存在一定差异， MB组对加州鲈鱼肌肉整体滋味贡献最大，这可为其在加州鲈鱼中应用提供理论依据。     

卤猪肉加工过程中游离脂肪酸、游离氨基酸及核苷酸变化分析

利用气相色谱质谱联用和高效液相色谱法检测分析了卤猪肉加工过程中游离脂肪酸、游离氨基酸及核苷酸的变化。结果表明,在加工过程中,总游离脂肪酸有效峰面积呈下降趋势,饱和脂肪酸也呈现下降的变化趋势,不饱和脂肪酸含量先增加后减少,在高温煮制1 h时达到最大值。总游离氨基酸的含量在卤猪肉加工过程中变化明显,在原料肉中总游离氨基酸含量为244.39 mg/100 g,其它样品中含量都显著(p0.05)高于原料肉,在二次煮制完成后达到最大值,为349.32 mg/100 g。谷氨酸在成品中的含量达到119.02mg/100 g,占总游离氨基酸的34.12%。呈味核苷酸检测结果显示,在加工过程中5'-IMP和5'-GMP的含量呈现下降趋势。由于加热导致核苷酸热降解,其降解产物肌苷的含量呈现上升趋势,在成品中检测到其含量显著(p0.05)高于原料肉中的含量。本研究结果为改进卤猪肉的生产工艺、提高产品品质提供了理论参考。     

电子束辐照对细点圆趾蟹肉营养及滋味成分的影响

以细点圆趾蟹蟹肉为材料,研究电子束辐照对蟹肉营养和滋味成分的影响,为电子束辐照技术在水产品加工中的应用提供依据。结果表明：辐照处理后7 kGy及以上剂量组蟹肉总氨基酸和非必需氨基酸含量下降比较明显;辐照没有改变蟹肉的第1和第2限制性氨基酸种类,各组蟹肉必需氨基酸与总氨基酸之比和必需氨基酸与非必需氨基酸之比均分别超过40%和60%,为质量较好的蛋白质;脂肪酸分析结果显示,电子束辐照对蟹肉饱和脂肪酸、单不饱和脂肪酸和多不饱和脂肪酸总量均无显著影响;随着辐照剂量增加,蟹肉中的游离氨基酸总量呈下降趋势,但呈鲜、甜鲜味的游离氨基酸含量有所增加,说明适当的辐照剂量对蟹肉氨基酸的呈味有改善作用;蟹肉中的主要呈味核苷酸是5’-肌苷酸二钠,辐照后蟹肉5’-腺苷酸和5’-肌苷酸二钠含量有所上升,而5’-鸟苷酸二钠含量有所下降,辐照对蟹肉鲜味有提升作用;结合鲜味氨基酸和呈味核苷酸的鲜味协同效应,各辐照组味精当量值均高于对照组,其中1 kGy组蟹肉的味精当量值最高,达到17.92%。综合蟹肉氨基酸、脂肪酸组成和滋味成分的变化规律分析,认为1～9 kGy剂量电子束辐照对蟹肉营养和滋味没有明显的负面影响,可用于对蟹肉进行前处理。