氢火焰离子气相色谱法测定焦糖色中的4-甲基咪唑

目的:建立氢火焰离子气相色谱法测定焦糖色中4-甲基咪唑含量的分析方法.方法:焦糖色用氢氧化钠溶液溶解,加乙腈萃取后,将有机相浓缩、定容后直接进样检测.结果:用乙腈萃取焦糖色中的4-甲基咪唑,样品加标回收率在95％以上,精密度为1.0％～1.3％.结论:该方法具有简便、快速、回收率高的优点,适用于焦糖色中4-甲基咪唑含量...     

低4-甲基咪唑焦糖色素制备工艺优化

为研究减少焦糖色素中4-甲基咪唑(4-Methylimidazole,4-MeI)生成的工艺,以葡萄糖为原料,碳酸铵为催化剂,利用高压反应制备4-甲基咪唑含量低、色率及红色素指数高的焦糖色素。采用正交试验设计考察了反应温度、反应时间、催化剂添加量(以NH₄+计)、葡萄糖液质量浓度四个因素对焦糖色素的色率、红色指数、4-甲基咪唑含量的影响。结果表明,利用综合平衡法确定生产参数为135 ℃、80 min、3% NH₄+及500 g/L 葡萄糖浓度,制备得到的氨法焦糖色素色率6.73×104 EBC,红色素指数5.21,4-甲基咪唑的含量198.34 μg/mL。通过对焦糖色素的生产工艺进行优化,得到了4-MeI明显降低的焦糖色素,为其生产提供了理论依据。     

沃特世提供整体解决方案分析饮料中2-甲基咪唑和4-甲基咪唑含量应用沃特世ACQUITY UPLC(R)H-CLASS-PDA系统和ACQUITY UPLC/Xevo(R)TQ MS系统

焦糖色素是一种允许使用的着色剂,我国对焦糖色素使用量的规定除个别产品外均为按生产需要适量使用,其中规定仅有亚硫酸铵法生产的焦糖色素允许使用在碳酸饮料中.而以加氨或其铵盐制成的焦糖(Ⅲ类氨法焦糖和Ⅳ类亚硫酸铵法焦糖)会产生4-甲基咪唑,并且4-甲基咪唑是一种能够诱发肿瘤的高水平化学物质.焦糖色素被广泛用于食品及饮料中,所以4-甲基咪唑的含量监控也是必须被重视的,由于4-甲基咪唑分子极性很大,含量很低,所以如何快速、准确地检测出其含量,就成为人们现阶段研究的重点.     

沃特世提供整体解决方案分析饮料中2-甲基咪唑和4-甲基咪唑含量 应用沃特世ACQUITY UPLCH-CLASS-PDA系统和ACQUITY UPLC/XevoTQ MS系统

焦糖色素是一种允许使用的着色剂,我国对焦糖色案使用量的规定除个别产品外均为按生产需要适量使用,其中规定仅有亚硫酸铵法生产的焦糖色素允许使用在碳酸饮料中。而以加氨或其铵盐制成的焦糖（Ⅲ类氨法焦糖和Ⅳ类亚硫酸铵法焦糖）会产生4-甲基咪唑,     

低4-甲基眯唑含量的焦糖色素制备工艺的研究

本文以精炼糖糖蜜为原料,采用氨法成功制备出低4-甲基咪唑含量的焦糖色素。通过单因素试验研究,确定了影响焦糖色素中4-甲基咪唑含量的主要因素及其合理的正交实验水平范围,再以正交实验确定制备低4-甲基咪唑含量焦糖色素的工艺为：反应温度115℃,反应时间90min,在反应过程中逐滴加入铵盐,铵盐添加量为6％。     

焦糖色素中4-甲基咪唑的液质联用检测方法的研究

建立测定焦糖色素中4-甲基咪唑的高效液相色谱-串联质谱(LC-MS/MS)分析方法。水溶解样品后,Waters Oasis MCX固相萃取柱为净化柱,ACQUITY BEH HILIC色谱柱(2.1 mm×100 mm,1.7μm)为分析柱,5mmol/L甲酸铵溶液和0.1%甲酸乙腈为流动相,电喷雾正离子多反应监测模式进行检测,内标法定量。试验结果表明:5~100μg/L范围内,4-甲基咪唑的浓度和峰面积线性关系良好。确定该方法的定量限为10mg/kg,检出限为3mg/kg。对未添加焦糖色的老抽中进行3个加标水平,4-甲基咪唑的回收率为99.7%~115.7%,变异系数均不超过3%。该方法的线性相关性良好,定量限和检出限低,精密度和准确度均符合要求,能够满足焦糖色素中4-甲基咪唑的检测要求。     

气相色谱串联三重四级杆质谱测定焦糖色中4-甲基咪唑

建立气相色谱-串联质谱(GC-MS/MS)测定焦糖色中4-甲基咪唑的检测方法。样品经过碱化处理,硅藻土固定吸附,乙酸乙酯直接萃取,气相色谱-串联质谱法多反应监测模式(MRM)测定。4-甲基咪唑在0.5～20μg/m L内具有较好线性关系,线性相关系数为0.999 7,方法检出限为5 mg/kg,在3个加标水平(5, 100和200 mg/kg)下加标回收率为78.3%～91.7%,相对标准偏差(RSD, n=6)为2.11%～7.12%,该方法前处理简单快捷,方法灵敏度高,准确性好,能够满足对焦糖色中4-甲基咪唑分析检测的需要。     

ZIC -HILIC色谱柱检测可乐饮料中的甲基咪唑

近日，百事可乐的产品在美国10个州中被爆出4-甲基咪唑（4-MethyIImidazole）严重超标。4-甲基咪唑是一种有机中间体．主要用于合成大宗胃药西咪替丁，也可用作环氧树脂固化剂和金属表面防护剂等。可乐中的4-甲基咪唑是在以亚硫酸铵为原料生产焦糖色素时产生的。4-甲基咪唑白色至类白色结晶粉末．易溶于水和乙醇，有腐蚀性．是一种能诱发肿瘤的化学物质。     

上海市粮油工业公司在沪召开《非氨法焦糖色的研制》技术鉴定会

上海市粮油工业公司于一九八三年九月七日在上海市主持召开了《非氨法焦糖色的研制》技术鉴定会议,出席会议单位有11个,代表25名。由于氨法焦糖色(俗称酱色)含有对人体有害的4-甲基咪唑,根据我国食品添加剂使用卫生标准规定,在食品中不得添加此类焦糖色。鉴于今年七月一日起试行《中华人民共和国食品卫生法》,上海市酿造科学研究     

焦糖色的生物,毒性试验概况及生产现状

焦糖色在1975年的至1985年的10年里,我国曾一度禁止使用过,原因是由于FAO/WHO(联合国粮农组织及世界卫生组织)食品添加剂专门委员会,发表文章称焦糖色在生产过程中生成4-甲基咪唑,认为有致惊厥作用。在此期间就酱油添加焦糖色的问题曾在学术上和业务上争论多年,各持己见,难以统一。事实上,我国南方很多单位在禁用期     

A U.S. population dietary exposure assessment for 4-methylimidazole (4-MEI) from foods containing caramel colour and from formation of 4-MEI through the thermal treatment of food

ABSTRACT

4-Methylimidazole (4-MEI) is formed in caramel colours produced using ammonium compounds (Class III and Class IV caramel colours). 4-MEI can also form in food through Maillard reactions between reducing sugars and amino acids during cooking, roasting or dry-heating. The USFDA has analysed over 700 food and beverage samples collected from 2013 to 2015 for the presence of 4-MEI. These samples include foods containing added caramel colour and foods that are not labelled as containing added caramel colour, but which may contain 4-MEI resulting from thermal treatment. The 4-MEI levels in all food samples were quantified using LC-MS/MS. These data were used to develop a comprehensive dietary exposure assessment for 4-MEI for the U.S. population aged 2 years or more and several sub-populations, using two non-consecutive days of food consumption data from the combined 2009–2012 National Health and Nutrition Examination Survey and 10–14-day food consumption survey data for 2009–2012 from the NPD Group, Inc. National Eating Trends–Nutrient Intake Database. Dietary exposure estimates were prepared for each category of foods labelled as containing added caramel colour and of foods not labelled as containing added caramel colour, but which may contain 4-MEI from thermal treatment. Exposure to 4-MEI from consumption of foods containing added caramel colour was higher than that from foods that contain 4-MEI from thermal treatment for all population groups. Cola-type carbonated beverages were the highest contributors for most populations from foods containing added caramel colour. Coffee was the highest contributor for most populations from foods in which 4-MEI could be formed from thermal treatment. An overall combined exposure to 4-MEI was also estimated that included all foods identified as containing added caramel colour and foods in which 4-MEI could be formed by thermal treatment.     

Dietary intake assessment of caramel colours and their processing by-products 4-methylimidazole and 2-acetyl-4-tetrahydroxy-butylimidazole for the Chinese population

ABSTRACT

The aim of the study was to assess the dietary intake of caramel colours and their by-products 4-methylimidazole (4-MEI) and 2-acetyl-4-tetrahydroxybutylimidazole (THI) for the Chinese population. Based on the typical and maximum reported use levels of caramel colours in 15 food categories, the dietary intakes of combined and single-class caramel colours of Classes I, III and IV were estimated with the food consumption data from the China National Nutrient and Health Survey. Using the mean values of 4-MEI and THI contents in Class III and Class IV Caramel colour samples, the exposures to 4-MEI and THI from dietary caramel colours were derived. The results showed that the combined and individual average dietary caramel colour intakes for the Chinese population of different age groups were estimated to be 232–60.3 mg kg^?1 bw day^?1 for combined caramels, 5.9–29.2 mg kg^?1 bw day^?1 for Class I, 7.7–29.6 mg kg^?1 bw day^?1 for Class III, 21.2–54.3 mg kg^?1 bw day^?1 for Class IV, which were far below the group acceptable daily intake (ADI) and respective ADIs. The combined intake of 4-MEI from Class III and IV caramel colours was estimated to be 3.8–5.2 μg kg^?1 bw day^?1 on average, and 12.9–27.1 μg kg^?1 bw day^?1 at 95th-97.5th percentile for the general population. The anticipated exposure to THI from Class III caramel colours was estimated to be 0.1–0.3 μg kg^?1 bw day^?1 on average and 0.5–1.7 μg kg^?1 bw day^?1 at 95th–97.5th percentile for the general population. The dietary caramel colours intakes and the exposures to 4-MEI and THI from dietary caramel colour for the Chinese population were considered to be of low health concern based on the present toxicological data. Soy sauce, vinegar and compound seasonings were found to be the main contributors to the dietary intake of caramel colours.     

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.     

焦糖色配方的工艺优化

为烹饪中的焦糖色标准化和科学化生产提供科学依据,对焦糖色的最优配方和制作工艺进行了研究。以感官评分为标准,通过单因素试验和响应面试验研究了白砂糖添加量、加热时间、沸水添加量的影响。确定焦糖色最佳制作配方和工艺条件为:白砂糖添加量为153.51 g,加热时间为8.91 min,沸水添加量为99.88 g。经此配方工艺制作的焦糖色感官评分高达98.7,具有焦香味浓郁,色泽呈深黑红棕色且富有光泽等特点。最后,以卤肉为载体,比较焦糖色与常用食品增色剂老抽酱油以及焦糖色和老抽酱油混合物(老抽:焦糖=1:1混合,m/m)对食品色泽参数包括亮度L*值、红度a*值、黄度b*值、彩度c*值的影响。结果表明,三种食品增色剂对卤肉的亮度L*值和黄度b*值和彩度c*值没有显著性差异(p>0.05),对卤肉的红度a*值差异显著(p<0.05),说明焦糖色能够提高卤肉的光泽度和红度,与感官评定结果一致。     

为焦糖色"正身" --浅谈食品添加剂之焦糖色

焦糖色作为允许使用的一种食品添加剂，其用途是十分广泛的，合格的焦糖色是以大米、蔗糖为原料，在高温高压和一定催化剂作用下，经美拉德(Maillard)反应生成的混合物，是一种稳定安全的产品。希望广大读者通过此文能够对焦糖色这一产品有一个客观公正的认识。     

Effect of Various Food Additives on the Levels of 4(5)‐Methylimidazole in a Soy Sauce Model System

In this study, the effect of food additives such as iron sulfate, magnesium sulfate, zinc sulfate, citric acid, gallic acid, and ascorbic acid on the reduction of 4(5)‐methylimidazole (4(5)‐MI) was investigated using a soy sauce model system. The concentration of 4(5)‐MI in the soy sauce model system with 5% (v/v) caramel colorant III was 1404.13 μg/L. The reduction rate of 4(5)‐MI level with the addition of 0.1M additives followed in order: iron sulfate (81%) > zinc sulfate (61%) > citric acid (40%) > gallic acid (38%) > ascorbic acid (24%) > magnesium sulfate (13%). Correlations between 4(5)‐MI levels and the physicochemical properties of soy sauce, including the amount of caramel colorant, pH value, and color differences, were determined. The highest correlations were found between 4(5)‐MI levels and the amount of caramel colorant and pH values (r² = 0.9712, r² = 0.9378). The concentration of caramel colorants in 8 commercial soy sauces were estimated, and ranged from 0.01 to 1.34% (v/v).     

分光光度法测定焦糖色中4-甲基咪唑

本采用分光光度法对焦糖色中4-甲基咪唑进行了定量测定，克服了传统薄层法的精密度、准确度不高的弱点。实验结果表明，4-甲基咪唑经重氮化后在波长440nm处具有最大吸收，据此进行准确定量测定，重现性好。该方法灵敏度高，其线性方程为：C=0．0717A 0．0007，线性相关系数为0．999，检出限为1．4μg，RSD为3．5N。加标回收率为96N～102％。将本法用于实际样品的测定获得满意的结果。     

4-Methylimidazol in Caramel und caramelgef?rbten Lebensmitteln

Zusammenfassung Es wird eine spezifische und kochempfindliche Methode zur Bestimmung von 4-Methylimidazol (4-MeI) in Caramel und caramelgefärbten Lebensmitteln beschrieben. Nach der Extraktion wird 4-MeI gaschromatographisch mit einem stickstoffspezifischen elektrochemischen Detektor (Hall) bestimmt. Als weniger spezifische Alternative kann ein thermoionischer Detektor eingesetzt werden. Bei Zusätzen von 5–200 mg 4-MeI/kg Karamel beträgt die Wiederfindungsrate 90–94%.Die Nachweisgrenze der Methode liegt unterhalb 0,1 mg 4-MeI/kg Caramel; in karamelgefärbten Lebensmitteln können weniger als 0,01 mg/kg nachgewiesen werden.

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4-methylimidazole in caramel and caramel-colored foodsDetermination by gas-liquid-chromatography with nitrogen-specific detectors

Summary A specific and highly sensitive method for the determination of 4-methylimidazole (4-MeI) in caramel and caramel-colored foods is described. After extraction the amount of 4-MeI is determined by gas-liquid chromatography with a nitrogen-specific electrochemical detector (Hall). As a less specific alternative a thermoionic detector can be used. With additions in the range of 5–200 mg 4-MeI/kg caramel, recoveries of 90–94% are obtained.The limit of detection is <0.1 mg 4-Mel/kg caramel; in caramel-colored foods less than 0.01 mg/kg can be detected.

     

常压制备焦糖色素的工艺研究

焦糖色素是广泛应用于食品工业中的天然着色剂。本文探讨了在常压下,以蔗糖为原料制备焦糖色素的工艺条件。通过单因素实验研究了蔗糖含量、pH值、催化剂的添加量和反应时间对焦糖色素色率(EBC)的影响,通过正交实验确定了制备焦糖色素的最佳反应条件。结果表明,各因素对焦糖色素色率的影响大小为:蔗糖含量催化剂添加量pH值反应时间;且蔗糖含量为60%,pH=5.0,添加催化剂6%的条件下反应9h,可制备出EBC达到29474、pH为4.28、耐盐性好、符合国标GB8817-2001色率要求的优质焦糖色素。