杂环胺分子印迹聚合物的制备及应用研究

发布时间：2018-03-20 14:07

本文选题：杂环胺　切入点：分子印迹技术　出处：《天津科技大学》2016年硕士论文　论文类型：学位论文

【摘要】：杂环胺不仅存在于经热加工的蛋白质食品尤其肉制品中,还存在于环境、人的体液、水等,人们每天都会接触到各种类型的杂环胺。杂环胺在肉制品中浓度很低,以ng g~(-1)级存在,并且存在的基质复杂,含有大量蛋白质、脂肪和其它杂质,大大限制了人们对杂环胺的研究与分析。但杂环胺具有强烈的致癌致突变性,长期接触对人体损伤很大。因此,杂环胺分析检测受到众多学者的关注。首先本论文采用液相色谱串联质谱法对北京、天津、石家庄三个地区24种烤肉和酱肉制品中的2-氨基-3-甲基咪唑[4,5-f]喹啉(IQ)、2-氨基-3,4-二甲基咪唑[4,5-f]喹啉(MelQ)、2-氨基-3,8-二甲基咪唑[4,5-f]喹喔啉(MeIQx)、2-氨基-3,4,8-三甲基咪唑[4,5-f]喹喔啉(4,8-DiMeIQx)、2-氨基~(-1)-甲基-6-苯基咪唑[4,5-b]吡啶(PhIP)进行了检测,比较了样品中三地总的杂环胺含量,结果表明北京地区实际样品中总的杂环胺含量最高,但石家庄地区实际样品产生的杂环胺种类更多。其次本论文采用表面印迹技术合成了对杂环胺具有吸附性能的分子印迹聚合物,以分子印迹聚合物作为固相萃取材料,与高效液相色谱-紫外检测器联用建立了五种杂环胺的分析检测方法。根据所选杂环胺目标物的结构,选取3-氨基-9-乙基咔唑(AEC)为假模板,在双键修饰后硅球表面,以甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂合成具有高选择性表面印迹聚合材料。通过优化不同的合成条件,得出最佳合成条件,并通过傅里叶红外光谱、电镜扫描、吸附平衡实验和吸附动力学实验进行表征,以评价分子印迹聚合物的形貌特征,吸附特性。将合成的表面印迹聚合材料作为固相萃取的吸附剂,通过优化上样溶剂、洗脱溶剂和洗脱体积得到最佳固相萃取条件。所建立的SPE-HPLC检测方法在最优条件下,五种杂环胺的线性范围为1~(-1)00μg L~(-1),相关系数均在0.99以上。方法检出限在0.31-0.55 μg L~(-1)范围内。将该法用于实际样品中,选取天津当地超市购得的烤鸭、猪肝和卤鸡腿,在烤鸭中可检测到MeIQ和MeIQx,浓度分别为2.739μg kg~(-1)和1.581μg kg~(-1);在猪肝中可检测到MeIQx为3.472μg kg~(-1);在卤鸡腿中可检测到浓度为2.265 μg kg~(-1)的PhIP。对三种实际样品进行低、中、高为20、40、60 μg kg~(-1)三种水平的加标回收实验,得到五种杂环胺的加标回收率在67.13%—111.37%范围内,RSD9.42%,说明本实验建立的方法是有效的,可用于实际样品的检测,具有一定的准确性和稳定性。
[Abstract]:Heterocyclic amines not only exist in hot processed protein foods, especially meat products, but also exist in environment, human body fluids, water, etc. People are exposed to various types of heterocyclic amines every day. The concentration of heterocyclic amines in meat products is very low. It exists in ng / g ~ (-1) grade, and the matrix is complex and contains a lot of protein, fat and other impurities, which greatly limits the research and analysis of heterocyclic amines. However, heterocyclic amines have strong carcinogenic mutagenicity. Long-term exposure has caused great damage to human body. Therefore, the analysis and detection of heterocyclic amines have attracted many scholars' attention. First of all, liquid chromatography tandem mass spectrometry (LC-MS) was used to determine the content of heterocyclic amines in Beijing and Tianjin. 2-Amino-3-Methyl-Imidazolam [45-f] Quinoline 2-Amino-3Amino-3Amidazolam [45-f] Quinoline MelQ-2-Amino-3-Amino-8-Dimethyl-Imidazolam [45-f] Oroquinoline-2-Amino-3-dimethyl Imidazolium [45-f] Oroquinoline-2-Amino-3-trimethyl Imidazolium. A method was developed for the determination of pyridine (PhIP) with methyl -6-phenylimidazole. The contents of total heterocyclic amines in the samples were compared. The results showed that the total heterocyclic amines in the real samples in Beijing were the highest. However, there are more kinds of heterocyclic amines produced in actual samples in Shijiazhuang area. Secondly, the molecularly imprinted polymers with adsorptive properties of heterocyclic amines were synthesized by surface imprinting technique, and molecularly imprinted polymers were used as solid phase extraction materials. Five analytical methods of heterocyclic amines were established by using high performance liquid chromatography-UV detector. According to the structure of the selected heterocyclic amines, 3-amino-9-ethylcarbazolium AECs were selected as false templates, and the surface of silica spheres was modified by double bonds. A highly selective surface imprinted polymerization material was synthesized by using MAA as functional monomer, ethylene glycol dimethacrylate (EGDMA) as crosslinking agent and azodiisobutyronitrile (AIBN) as initiator. The optimum synthesis conditions were obtained and characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), adsorption equilibrium experiment and adsorption kinetics experiment to evaluate the morphology of the molecularly imprinted polymer. Adsorption properties. The synthesized surface imprinted polymeric materials were used as adsorbents for solid phase extraction. The optimal conditions of solid phase extraction were obtained by optimizing the sample solvent, eluting solvent and elution volume. The linear range of the five kinds of heterocyclic amines was 1g / L ~ (-1) and the correlation coefficient was above 0.99. The detection limit of the method was 0.31-0.55 渭 g / L ~ (-1). The method was applied to the practical samples and selected roast duck, pig liver and brine chicken legs purchased from local supermarkets in Tianjin. MeIQ and MeIQX were detected in roast duck (2.739 渭 g / kg) and 1.581 渭 g / kg / kg / 1C respectively; MeIQx was 3.472 渭 g / kg / kg ~ (-1) in pig liver; and 2.265 渭 g / kg ~ (-1) in chicken leg. The recovery rate of five heterocyclic amines was in the range of 67.13- 111.37%. The results showed that the method established in this experiment is effective and can be used for the detection of real samples with certain accuracy and stability.
【学位授予单位】：天津科技大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631.3;TS251.7

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