Formation of 4(5)‐Methylimidazole in Aqueous d‐Glucose‐Amino Acids Model System

The International Agency for Research on Cancer (IRAC) has classified 4(5)‐methylimidazole (4‐MeI) as a group 2B possible human carcinogen. Thus, how 4‐MeI forms in a d ‐glucose (Glu) amino acids (AA) model system is important, as it is how browning is affected. An aqueous solution of Glu was mixed individually in equimolar amounts at 3 concentrations (0.05, 0.1, and 0.15 M) with aqueous solutions of l ‐Alanine (Ala), l ‐Arginine (Arg), Glycine (Gly), l ‐Lysine (Lys), and l ‐Serine (Ser). The Glu‐AA mixtures were reacted at 60, 120, and 160 °C for 1 h. The 4‐MeI levels were measured by gas chromatography‐mass spectrometry after derivatization with isobutylchloroformate. No 4‐MeI was formed at 60 °C for any treatment combination; however, at 120 °C and 0.05 M, Glu‐Arg and Glu‐Lys produced 0.13 and 0.14 mg/kg of 4‐MeI. At 160 °C and 0.05 M all treatment combinations formed 4‐MeI. At 160 °C and 0.15 M, the observed levels of Glu‐Ala, Glu‐Arg, Glu‐Gly, Glu‐Lys, and Glu‐Ser were 0.21, 1.00, 0.15, 0.22, and 0.16 mg/kg. The AA type, reactant concentrations, and temperature significantly affected (P < 0.001) formation of 4‐MeI as well as browning. Glu‐Lys treatment in all combinations produced the most browning, but Glu‐Arg produced the most 4‐MeI. This method showed that foods processed using low temperatures may have reduced levels of 4‐MeI.     

Detection and Quantification of 4(5)‐Methylimidazole in Cooked Meat

4(5)‐Methylimidazole (4‐MeI) is a nitrogen‐containing heterocyclic compound found in class III and IV ammoniated caramel colors, a group of additives widely used in the food industry. A suspected carcinogen and neurotoxin and efforts are underway to limit its presence in foods. Several methods have been developed to detect and quantitate 4‐MeI in different food matrices, including roasted coffee, beer, soft drinks, and soy sauce; however, no methods are available to measure 4‐MeI in cooked meat and meat products containing lipids and high levels of interfering nitrogen compounds, such as amino acids and peptides. A rapid method using 0.1 M sodium acetate buffer (pH 5) as an extraction solvent followed by derivatization with isobutylchloroformate and gas chromatograph mass‐spectrometry was developed to quantify 4‐MeI in cooked meat products with added caramel colors containing 4‐MeI. Selected ion monitoring mode was used to monitor 4‐MeI ions fragments. In the 8 commercial meat products tested, 4‐MeI levels ranged from 0.041 to 1.015 mg/kg, with recovery of 94.76% to 103.94%. In addition, a matrix‐matched calibration performed by analyzing a spiked cooked meat sample indicated no significant difference (P > 0.05), which means the meat matrix had no effect on the developed method. This method proved useful in analyzing 4‐MeI in meat products with added caramel color containing 4‐MeI.     

3‐Chloropropane‐1,2‐diol (3‐MCPD) in Soy Sauce: A Review on the Formation,Reduction, and Detection of This Potential Carcinogen

Soy sauce, a dark‐colored seasoning, is added to enhance the sensory properties of foods. Soy sauce can be consumed as a condiment or added during the preparation of food. There are 3 types of soy sauce: fermented, acid‐hydrolyzed vegetable protein (acid‐ HVP), and mixtures of these. 3‐Chloropropane‐1,2‐diol (3‐MCPD) is a heat‐produced contaminants formed during the preparation of soy sauce and was found to be a by‐product of acid‐HVP‐produced soy sauce in 1978. 3‐MCPD has been reported to be carcinogenic, nephrotoxic, and reproductively toxic in laboratory animal testing and has been registered as a chemosterilant for rodent control. 3‐MCPD is classified as a possible carcinogenic compound, and the maximum tolerated limit in food has been established at both national and international levels. The purpose of this review is to provide an overview on the detection of 3‐MCPD in soy sauce, its toxic effects, and the potential methods to reduce its concentration, especially during the production of acid‐HVP soy sauce. The methods of quantification are also critically reviewed with a focus on efficiency, suitability, and challenges encountered in analysis.     

乙醇对酱油发酵体系中蛋白酶系的影响研究

通过控制酒精发酵来研究乙醇对酱油发酵体系中蛋白酶系的影响,发现乙醇对碱性蛋白酶的稳定性影响很大,特别是在发酵温度为30℃、pH 5.0、乙醇含量在2％以上时碱性蛋白酶失活加剧;乙醇对中性蛋白酶活力的抑制作用较明显,特别是在乙醇含量大于2％以后,其活力急剧下降,最低降到38％.研究结果显示,适度的酒精发酵对氨基氮生成和原...     

炒制温度对酱油游离氨基酸变化规律的影响

研究了100,160,220℃3种常用炒制温度对酱油游离氨基酸变化规律的影响。结果表明:随着炒制温度的升高,酱油中的鲜味氨基酸浓度逐渐增加。未处理和100℃炒制处理酱油中TAV>1的游离氨基酸均有9种,而160,220℃炒制处理酱油中TAV>1的游离氨基酸均有12种。100,160,220℃炒制处理后,分别有15,12,9种游离氨基酸含量增多,1,4,6种游离氨基酸含量减少。100,160℃炒制处理后酱油中游离氨基酸总量均增多,220℃炒制处理后酱油中游离氨基酸总量减少。100,160,220℃炒制处理后酱油中必需氨基酸总量均增多。100,160,220℃炒制处理后酱油中杂环氨基酸、非极性氨基酸、碱性氨基酸和疏水性氨基酸总量均增多,而脂肪族氨基酸、芳香族氨基酸、极性氨基酸、酸性氨基酸和亲水性氨基酸总量在100,160℃炒制处理后均增多,但在220℃炒制处理后其总量均减少。     

Simple and Fast Sample Preparation Followed by Gas Chromatography‐Tandem Mass Spectrometry (GC‐MS/MS) for the Analysis of 2‐ and 4‐Methylimidazole in Cola and Dark Beer

We have developed a simple and fast sample preparation technique in combination with a gas chromatography‐tandem mass spectrometry (GC‐MS/MS) for the quantification of 2‐methylimidazole (2‐MeI) and 4‐methylimidazole (4‐MeI) in colas and dark beers. Conventional sample preparation technique for GC‐MS requires laborious and time‐consuming steps consisting of sample concentration, pH adjustment, ion pair extraction, centrifugation, back‐extraction, centrifugation, derivatization, and extraction. Our sample preparation technique consists of only 2 steps (in situ derivation and extraction) which requires less than 3 min. This method provided high linearity, low limit of detection and limit of quantification, high recovery, and high intra‐ and interday repeatability. It was found that internal standard method with diluted stable isotope (4‐MeI‐d₆) and 2‐ethylimidazole (2‐EI) could not correctly compensate the matrix effects. Thus, standard addition technique was used for the quantification of 2‐ and 4‐MeI. The established method was successfully applied to colas and dark beers for the determination of 2‐MeI and 4‐MeI. The 4‐MeI contents in colas and dark beers ranged from 8 to 319 μg/L and from trace to 417 μg/L, respectively. Small quantity (0 to 8 μg/L) of 2‐MeI was found only in dark beers. The contents of 4‐MeI (22 μg/L) in colas obtained from fast food restaurants were significantly lower than those (177 μg/L) in canned or bottled colas.     

铁强化酱油对铁缺乏不贫血学生注意力和学习成绩的干预效果

观察乙二胺四乙酸铁钠(NaFeEDTA)强化酱油干预对铁缺乏不贫血(iron deficiency without anemia,IDNA)学生注意力和学习成绩的影响.以血红蛋白(Hb)值、血清铁蛋白(SF泄为指标将受试者分成正常(NA)组、铁缺乏不贫血(IDNA)组,观察NaFeEDTA强化酱油对IDNA、注意力和学...     

Analysis and risk assessment of 4(5)-methylimidazole in brown colored foods and beverages

In this study, the 4(5)-methylimidazole (4(5)-MI) levels in various 144 brown coloured foods and beverages were determined. The brown coloured foods and beverages were 62 processed sauces, 40 coffee, 9 caramel syrups, 18 red ginseng juice and 15 Japanese apricot fruit juice. The amount of 4(5)-MI in brewed coffee (1821.3 ng/g) was the highest level among the samples. The 4(5)-MI concentration in processed sauce (47.6 ng/g) was the lowest level among the samples. The levels of 4(5)-MI in various samples were found as follows: 47.6–1748.5 ng/g in processed sauces, 64.1–1821.3 ng/g in commercial coffee, 115.5–491.9 ng/g in caramel syrups, 91.0–854.1 ng/g in red ginseng juice and 137.6–587.4 ng/g in Japanese apricot fruit juice. Based on the 4(5)-MI levels, the estimated daily intake (EDI) and chronic daily intake (CDI) were calculated. EDI and CDI of red ginseng juice was the highest among all samples, and they were 1618.6 and 1256.8 ng/kg bw/day, respectively.     

Candida etchellsii产2(5)-乙基-4-羟基-5(2)-甲基-3(2H)-呋喃酮的影响因素

在埃切假丝酵母(Candida etchellsii)发酵过程中,通过盐度调控和氨基酸添加,强化目标产物HEMF(2(5)-乙基-4-羟基-5(2)-甲基-3(2H)-呋喃酮)的合成效率。分阶段调控发酵体系的盐度(初始阶段控制CaCl浓度为200 g/L,发酵40 h后提升至220 g/L),结合氨基酸添加(向发酵体系中添加丙氨酸、精氨酸和甘氨酸各1.67 g/L)。摇瓶结果表明:酵母C.etchellsii合成HEMF,其产量为110.74 mg/L。7 L发酵罐上罐验证,HEMF产量达到121.51 mg/L,相比空白(200 g/L CaCl浓度下且没有添加氨基酸)提高了21.2倍。分阶段盐度调控结合氨基酸添加策略显著强化了C.etchellsii对HEMF的合成。     

Effects of oxidised linoleic acid on the formation of Nε‐carboxymethyl‐lysine and Nε‐carboxyethyl‐lysine in Maillard reaction system

This study investigated the effects of oxidised linoleic acid (18:2) on N^ε‐carboxymethyl‐lysine (CML) and N^ε‐carboxyethyl‐lysine (CEL) formation in Maillard reaction systems. Model systems of lysine/glucose (L/G), lysine/18:2 (L/18:2), lysine/18:2/glucose (L/18:2/G), myofibrillar protein/glucose (MFP/G), MFP/18:2 and MFP/18:2/G were maintained at 37 °C for 6 weeks. The results showed that CML/CEL contents in L/G (6.99 and 0.96 mmol mol^?1 lysine, respectively) were significantly higher than those in L/18:2/G (1.43 and 0.41 mmol mol^?1 lysine, respectively), and there is a small amount of CML/CEL generation in L/18:2. However, the CML/CEL levels in MFP/G (197.2 and 83.8 ng mg^?1 protein, respectively) were markedly lower than those in MFP/18:2/G (283.2 and 118.5 ng mg^?1 protein, respectively). 18:2 favours the formation of CML/CEL in MFP/18:2/G, not in L/18:2/G. All these findings indicated that the role of 18:2 on CML/CEL formation in Maillard reaction system was complex, and depended on CML/CEL formation rate and substrate types (lysine or lysine residue in protein).     

The influence of mash pre-aging on the development of the flavour-active compound, 4-hydroxy-2(or5)-ethyl-5(or2)-methyl-3(2H)-furanone (HEMF), during soy sauce fermentation

Inoculation of Zygosaccharomyces rouxii into a soy sauce mash free from lactic acid bacteria at 10⁶ cells mL⁻¹ resulted in the formation of the flavour-active compound HEMF over a number of days at 30°C. Delays in inoculation up to 14 days after production of the mash greatly increased the amount of HEMF formed and under some conditions concentrations in the commercial range were achieved without addition of any other microorganisms.     

5-(4-(2-甲氧二氧)苯烯)-2-硫代噻唑-4-酮对雪莲果中酪氨酸酶的抑制作用

通过分光光度法探究5-(4-(2-甲氧二氧)苯烯)-2-硫代噻唑-4-酮(MBTO)对雪莲果中酪氨酸酶的抑制作用。结果表明：MBTO对雪莲果中酪氨酸酶有良好的抑制作用。单因素试验最佳抑制剂浓度为30.0μmol/L、最佳作用时间为210s、最佳作用温度为30℃。通过三因素三水平正交试验,分析得最佳反应条件为：pH7.5、抑制剂MBTO浓度30.0μmol/L、作用时间330s、作用温度30℃,可达到最佳抑制效果,在此条件下MBTO对雪莲果中酪氨酸酶的抑制率达84.24%。     

Simultaneous Analysis of Nε‐(Carboxymethyl)Lysine and Nε‐(Carboxyethyl)Lysine in Foods by Ultra‐Performance Liquid Chromatography‐Mass Spectrometry with Derivatization by 9‐Fluorenylmethyl Chloroformate

Isotope dilution ultra‐performance liquid chromatography–electrospray tandem mass spectrometry with derivatization by 9‐fluorenylmethyl chloroformate was successfully applied to quantify N^ε‐(carboxymethyl)lysine (CML) and N^ε‐(carboxyethyl)lysine (CEL) in processed foods. We demonstrate that this analytical method is well validated for the determination of CML and CEL contents in processed foods. Relative standard deviations (RSD) indicate repeatability (RSD < 6% for CML and CEL) and reproducibility (RSD < 6% for CML and < 7% for CEL) in this method. Percent recovery is also good. We obtain recoveries of 102% to 112% for CML and 86% to 114% for CEL. CML levels detected in the samples vary from 2.29 to 480 mg/kg food, whereas CEL is detected in significantly lower concentrations ranging from 0.56 to 107 mg/kg food. These data could help consumers make better food choices by monitoring intake of advanced glycation end‐products, which may pose a risk to human health.     

铅与meso-四(4-磺酸苯基)卟啉的显色系统研究及其在食品中铅的检测应用

本文采用吸光光度法,研究并优化了了铅与水溶性络合剂meso-四(4-磺酸苯基)卟啉(TPPS4)的显色条件,实验表明,在碱性条件(pH12)下,用邻二氮菲、硫氰酸铵、酒石酸钾钠作联合掩蔽剂,盐酸羟胺作辅助络合剂,铅与TPPS4需12min即可生成淡紫色络合物,该络合物的吸收峰为465nm,络合比为1:1。当铅含量在0～0.2μg/ml范围内时,萃取曲线符合比尔定律,用APDC/MIBK体系萃取样品中的铅离子,与TPPS4络合后比色测定几种食品中的铅,结果可行。     

3-苯基-4-氨基-5-硫酮-1,2,4-三唑对牛蒡中酪氨酸酶的抑制作用

以3-苯基-4-氨基-5-硫酮-1,2,4-三唑(APTT)为效应物,通过SPSS设计正交试验,研究不同APTT浓度、时间以及温度对牛蒡酪氨酸酶提取液的护色效果的影响,并探讨pH值对抑制剂及反应体系作用效果的影响,数据用SPSS软件处理,在25℃条件下,牛蒡与APTT比为0.5:3(g/mL)时,500μmol/L抑制剂对底物作用420s为最佳抑制反应条件,其ΔA为0.0082:pH7.0时,抑制效果最佳。APTT对牛蒡中酪氨酸酶有良好的抑制作用。     

Reversible Regulation of Gelatinization of Potato Starch with Poly(ε‐lysine) and Amino Acids

Poly(ε‐lysine) (PL), lysine (Lys), monosodium glutamate (GluNa), glycine (Gly), alanine (Ala), and leucine (Leu) were used to regulate the characteristic gelatinization behavior of potato starch. As determined by differential scanning calorimetry, PL, Lys, and GluNa with positive or negative net charge elevated the gelatinization temperature with increasing amount added as compared with the small effect of Gly, Ala, and Leu with zero net charge. The peak viscosity evaluated by a Rapid Viscoanalyser was markedly decreased by adding PL, Lys, and GluNa, whereas Gly and Ala had no effect on the peak viscosity. The swelling was also decreased by added PL, Lys, and GluNa, whereas it was unchanged by added Gly, Ala, and Leu. Potato starch immersed in PL or amino acid solution released most of the retained PL and amino acids by the subsequent washing with water. The increased gelatinization temperature of the PL‐treat­ed potato starch returned to the original value by washing with water. It is thus considered that the regulatory effects of PL and amino acids on the gelatinization behavior of potato starch were substantially reversible.     

Formation of 4‐hydroxynonenal (4‐HNE) in frozen mackerel (Scomber scombrus) in the presence and absence of green tea

BACKGROUND: Aldehydes are secondary lipid oxidation products formed during processing and storage of food. 4‐Hydroxynonenal (4‐HNE) is a major toxic lipid peroxidation product which has been extensively investigated in the clinical field but less so in food products. The aim of the present study was to investigate the formation of aldehydes in stored frozen fish (Atlantic mackerel, Scomber scombrus) with and without antioxidant (green tea). RESULTS: The presence of 4‐HNE in frozen fish was detected for the first time. 4‐HNE was extracted from frozen fish and identified using high‐performance liquid chromatography and liquid chromatography/mass spectrometry. The amount of 4‐HNE increased throughout storage for 26 weeks at ? 10 °C in the absence of antioxidant. A significant decrease was observed in fish samples stored at ?10 °C with green tea. Minimal amounts of 4‐HNE were formed in fish stored at ?80 °C. A similar increase in 4‐HNE was found for methyl linoleate and extracted fish oil exposed to UV irradiation. CONCLUSION: The toxic aldehyde 4‐HNE can be formed in badly stored frozen mackerel and is an indicator of reduced texture quality and nutritional value of fish. Addition of instant whole green tea as an antioxidant can provide a cheap and effective way of enhancing safety, especially in developing countries. Copyright © 2008 Society of Chemical Industry     

Meso-四-(3,5-二溴-4-羟基苯)卟啉光度法检测食品包装材料铅污染

研究了Ｍｅｓｏ－四－（３，５－二溴－４－羟基苯）卟啉［Ｔ（ＤＢＨＰ）Ｐ］与铅的显色反应，建立了一种测定食品包装材料铅污染的分析方法。在０．０８ｍｏｌ／ＬＮａＯＨ介质中，铅与Ｍｅｓｏ－四－（３，５－二溴－４－羟基苯）卟啉形成１２黄色配合物，最大吸收波长为４７９ｎｍ，表观摩尔吸光系数为２．２×１０５．研究表明，体系中加入８－羟基喹啉和盐酸羟胺，既加快了显色反应速度，在常温下放置５ｍｉｎ即可完成，又大大提高测定铅的选择性，能满足复杂体系中痕量铅的测定。