摘要
食品中外源添加物的安全性是食品安全的重要组成部分,随着现代食品工业的快速发展,食品添加剂的地位日益突出；然而,食品添加剂滥用甚至违法使用非法添加物的情况和食品安全事件时有发生,严重危害和影响人们的健康和社会稳定。
由于食品添加剂种类繁多,目前一种标准分析方法只能针对某几种特定目标物进行检测,不易实现对多种类添加物的同时检验分析,因此,有必要建立一种食品中外源添加物的筛查分析方法,对食品中的添加剂进行有效地监测,并对可能存在的非法添加现象进行预警。
本文以食品中外源添加物为对象,运用多种分析技术和手段,系统地开展了筛查分析技术方面的研究工作,主要研究内容及结果如下：
1.以奶酪样品为试验模型,建立了奶酪样品中46种禁限用合成色素的分级提取净化方法,并采用反相高效液相色谱多波长检测对该方法的效果进行了评价。样品的第一级提取净化采用正己烷振荡提取、凝胶渗透色谱净化,实现了对苏丹类染料的有效提取分离；第二级采用水振荡提取,乙腈辅助提取的手段,实现了对大多数水溶性合成色素及工业染料的提取分离；第三级则采用甲醇-氨水振荡提取,可实现对少数极性较强染料的提取分离。经过第二、三级提取后的样品,无需再净化,即可直接进行高效液相色谱分析,缩短了样品的前处理时间,提高了分析工作的效率。添加回收试验结果表明,该方法可用于多种食品基质中不同极性特征的46种禁限用合成色素的检测分析,具有较强的适用性和优越性。
2.对人造奶油中苏丹类染料化合物的液相色谱/四极杆-飞行时间质谱筛查检测方法进行了研究。样品经正己烷振荡提取和凝胶渗透色谱净化,液相色谱分离后采用四极杆-飞行时间质谱(LC/Q-TOF)进行分析,8种化合物的检测限在0.75 ng/mL～5 ng/mL之间；通过飞行时间质谱的精确质量数功能与谱图数据库检索,对8种苏丹类染料化合物进行了精确的匹配和鉴定,除苏丹红G外,其余化合物的匹配度均在94%以上,并通过二级质谱实现了化合物结构的确证。
3.对奶酪样品中29种禁限用合成色素的筛查方法进行了研究。样品经正己烷-水(3：1,V/V)振荡提取,乙腈二次提取,氨水-甲醇三次提取,正己烷提取液经凝胶渗透色谱去除油脂,乙腈-水相和氨水-甲醇不需净化直接分析。结果表明：29种不同极性范围的合成色素化合物分别得到了有效的提取,提取回收率为70%～95%；四极杆-飞行时间质谱的精确质量数定性功能可以将不同种类的合成色素化合物筛查出来,各化合物匹配度为60～99.5；通过Target MS/MS扫描方式进行定量,得到苏丹类化合物检测方法的检测限为0.4ng/g～2.5 ng/g之间,21种水溶性合成色素及染料化合物的检测限在0.02 mg//kg～0.10 mg/kg之间。该方法对禁限用合成色素的筛查范围比较宽泛,对含有蛋白质、脂肪等基质的食品具有较好的适用性。
4.采用以奶酪样品为模型的分级提取与净化样品前处理方法,以及液相色谱/四极杆-飞行时间质谱(LC/Q-TOF)技术对肉制品中的人工合成着色剂进行了筛查分析。筛查结果显示,部分肉制品中含有合成色素诱惑红。由此建立了固相萃取-液相色谱/三重四极杆串联质谱对肉制品中诱惑红的定量分析方法：样品经乙醇-氨水提取,正己烷脱脂后,利用以硅胶键合壳聚糖为吸附材料的固相萃取柱进行净化,优化后的固相萃取柱装填量为0.25 g,净化条件为6 mL甲醇淋洗,8 mL体积分数为2%的氨水-甲醇溶液洗脱,样品经液相色谱串联质谱测定(LC/MS/MS)。结果表明,采用此方法检测肉制品中诱惑红的含量,回收率高于70%。
5.对虾片中食品添加剂、非特定目标添加剂及未知物的筛查与分析方法进行了研究。利用液相色谱/四极杆-飞行时间质谱和电感耦合等离子体质谱(ICP-MS),实现了对样品中柠檬黄、胭脂红、日落黄、亮蓝以及铝残留量的筛查分析；利用四极杆-飞行时间质谱筛查出样品中含有未标识的苯甲酸和2,5-二特丁基对苯二酚；利用气相色谱-质谱联用技术(GC/MS)对油炸样品后的植物油进行分析,得到植物油中含有抗氧化剂叔丁基对苯二酚及其氧化产物,但未在食用油中发现虾片经油炸处理后产生的可疑化合物；通过比对和分析样品经微波及油炸处理前后的化合物信息,结果显示,在经微波、油炸后样品中添加剂未发生明显变化。研究结果表明,采用多仪器手段构建的筛查分析方法,适用于常用食品添加剂及食品中可疑化合物的检测分析及筛查确证。
The safety of exogenous additives was a significant part of food safety. The use of food additives became an important feature of modernization with the development of food industry. Otherwise, a few of food safety incidents occurred because of the abuse of food additives and illegal additives, which had a negative influence to the human healthy and the stability of society.
At present, a standard analytical method was usually fit for the detection of several targeted compounds and was difficult to determine multi-additives at the same time. Then it was necessary to establish an analytical method of exogenous additives to screen and warn the addition of food additives and potential illegal additives in food stuffs.
This paper developed the screening and analytical technology taking the exogenous additives as study object by multi analysis methods. The main research contents and results were as follows:
1. A method of sequential extraction and purification coupled with high performance liquid chromatography (HPLC) by multi-wavelength detection applied for the analysis of 46 synthetic pigments and dyes in food was established. The system of sequential extraction was composed of three grades. In the first grade of extraction, the Sudan dyes were extracted with n-hexane and purified effectively by Gel Permeation Chromatography (GPC). The recoveries of 8 Sudan dyes were not less than 80%. In the second grade of extraction, most of water-solution synthetic pigments were extracted with water assisted by acetonitrile. And the recoveries were not less than 60%. In the third grade of extraction, a few of compounds were extracted using methanol and ammonia water whose concentration was 1.0%. And the recoveries were not less than 55%. It was unnecessary to clean up the extract after the second and third grade of extraction. The detection results of samples from markets showed that the system of sequential extraction and cleaning was suitability for the food stuffs contained protein and fat.
2. A method of screening and determination Sudan dyes in margarine by high performance liquid chromatography/quadruple time-of-flight mass spectrometry (HPLC/Q-TOF) was established. The compounds were extracted by n-hexane and purified by GPC. The limit of detection of 8 kinds of Sudan dyes was between 0.75 ng/mL - 5 ng/mL analyzed by HPLC/Q-TOF.8 kinds of Sudan dyes were matched and identified by the function of precision mass searching and the mass spectrum library searching. The results displayed that the matching scores of all of dyes were high than 94%except Sudan red G. Then the compounds were confirmed by the Q-TOF mass spectrum.
3. A screening method of 29 forbidden and limited synthetic pigments was established by HPLC/Q-TOF in cheese samples. The pigments were extracted by n-hexane-water (3:1, V/V), acetonitrile, ammonia water-methanol (1:99, V/V) sequentially and purified by GPC. The results shown that 29 synthetic pigments with a wide range of polarity were extracted effectively whose recoveries were between 70 %-95%, and matched good by the function of precision mass searching and the mass spectrum library searching whose match scores were between 60-99.5. The quantitative analysis of 29 compounds was carried on by mode of Target MS/MS. The limit of detection (LOD) of 8 Sudan dyes were between 0.4 ng/g and 2.5 ng/g while the LOD of 21 water-soluble synthetic pigments were between 0.02 mg//kg-0.10 mg/kg. The screening method was suitable for a wide range of polarity and the food stuff with the similar matrix.
4. The synthetic colorants in meat products were screened by the sequential extraction and purification coupled with HPLC/Q-TOF. Allura red was found by this screening method. Then a determination of allura red in meat products by solid phase extraction with bonded Si-Chitosan as sorbent and liquid chromatography tandem mass spectrometry was established. Meat products were extracted by ethanol-ammonia water and the fat component was removed by n-hexane. Then the extraction solution was purified by solid phase extraction (SPE) with bonded Si-Chitosan as adsorption materials. The SPE conditions were optimized and the results as follows:the mass of bonded Si-Chitosan was 0.25 g, the washing solvent was 6 mL of methanol and the elution solvent was 8 mL of 2%ammonia water-methanol. The recoveries of analysis were higher than 70%, and the relative standard deviation (RSD) was between 3%to 7%.
5. A screening method of food additives and their potential cooking decomposition compounds was established in prawn crackers. As target additives, tartrazine, ponceau 4R, sunset yellow and brilliant blue were detected by HPLC/Q-TOF. As non-targeted additives, benzoic acid and 2,5-Di-tert-butylhydroquinone (BHQ) were found by this screening method. TBHQ and its oxidation product 2-tert-Butyl-l,4-benzoquinone were found by GC/MS. Prawn cracker samples were treated with microwave and were fried by edible oil respectively. And the chromatograms of them were compared with untreated samples using HPLC/Q-TOF. The results showed that there were no typical suspicious substances originated from additives during the cooking process. And the effectiveness of the screening system reflected that it was suitable to detect, analyze, screen and confirm food additives and suspicious compounds in food matrix.
引文
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