表面增强拉曼散射光谱在限定食品添加剂中的应用
发布时间：2018-07-17 08:18
【摘要】：食品添加剂的使用极大丰富了人们的物质饮食文化。然而对于零售散装食品面临着监管控制困难的情况,不法商人在食品中违法滥用添加剂,这不仅会损害了消费者的权益还危害着消费者的健康。研究表明,胭脂红作为一种偶氮类色素会导致DNA损伤诱发突变,邻苯甲酰磺酰亚胺作为添加剂的安全性目前仍然存在争议,食用油中的乙基麦芽酚香精的发现则意味着食用油品质和安全的降低,而如果长期过量食用这些含有乙基麦芽酚的食用油还会导致头痛呕吐等症状。完善的样品处理及检测技术可以帮助我们及时发现食品安全存在的问题。目前,针对不同样品的检验方法有气相色谱法(GC)、高效液相色谱法(HPLC)、质谱联用法(GC-MS)、液相色谱—质谱联用法(LC-MS)这类“黄金标准”,这些检验方法往往存在前处理繁琐、操作条件复杂、仪器笨重昂贵等缺点,而不适合于现场快速分析检测。与传统的拉曼光谱相比表面增强拉曼光谱(SERS)克服了它低灵敏度的缺点,能提供结构特征性强的分子水平信息,在用于痕量样品的分析检测中发挥了重要作用。表面增强拉曼光谱应用的一个重要环节就是制备能增强拉曼信号的SERS基底。金、银纳米粒子,其中金属纳米由于其固有的表面等离子体共振效应,常作为SERS增强基底。在制备的纳米粒子的过程中加入一定量的保护剂可有效阻止纳米粒子的团聚,提高纳米粒子的稳定性。本文进行尝试性研究,将拉曼光谱技术应用于食品安全检测中,对茶饮中胭脂红、冬枣中的邻苯甲酰磺酰亚胺和食用油中乙基麦芽酚进行测定,试图建立起简便、快速的不良食品添加剂的检测新方法,进一步扩大拉曼光谱的使用范围,为拉曼光谱在食品安全检测发展中打下良好基础。主要研究内容和结果如下:1、通过改变激发光激发波长降低样品荧光背景信号,对三种红色色素胭脂红,罗丹明B以及罗丹明6G进行同时测定,能够显著区分三种物质并能同时测定。2、通过引入植酸钠保护剂对制备的金属Ag纳米粒子进行修饰,该方法简单快捷,稳定性良好,以R6G为探针分子,SERS增强性能良好,可用于检测冬枣中的邻苯甲酰磺酰亚胺。3、引入Fe~(3+)为媒介并采用功能化金纳米粒子对挥发性乙基麦芽酚进行检测,实现可视化-散射光谱两种方式鉴别食品中的乙基麦芽酚,方法简单快捷。本论文研究结果表明,采用拉曼光谱技术对茶饮中胭脂红、冬枣中邻苯甲酰磺酰亚胺、食用油中乙基麦芽酚进行检测,实验结果较理想,具有一定的现实推广价值。说明拉曼光谱作为一种快速、无损、安全的检测技术,在食品安全检测中具有一定的应用前景和市场潜力。
[Abstract]:The use of food additives has greatly enriched people's material diet culture. However, it is difficult to supervise and control retail bulk food. Illegal merchants abuse additives illegally in food, which not only damages the rights and interests of consumers, but also harms the health of consumers. The results show that rouge, as an azo pigment, can lead to DNA damage induced mutation, and the safety of o-benzoyl sulfonimide as an additive is still controversial. The discovery of ethyl maltol in edible oils means a decrease in the quality and safety of edible oils, which can also lead to symptoms such as headache and vomiting if the edible oils contain ethyl maltol for a long period of time. Perfect sample handling and testing technology can help us to find food safety problems in time. At present, the methods for the determination of different samples are gas chromatography (GC), high performance liquid chromatography (HPLC), mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The operation condition is complex, the instrument is heavy and expensive, but is not suitable for the field rapid analysis and detection. Surface-enhanced Raman spectroscopy (SERS) overcomes the disadvantages of low sensitivity and can provide molecular level information with strong structural characteristics. It plays an important role in the analysis and detection of trace samples. The preparation of SERS substrate which can enhance Raman signal is an important step in the application of surface-enhanced Raman spectroscopy. Gold and silver nanoparticles, among which metal nanoparticles are often used as SERS enhancement substrates due to their inherent surface plasmon resonance effect. Adding a certain amount of protective agent in the process of preparation of nanoparticles can effectively prevent the agglomeration of nanoparticles and improve the stability of nanoparticles. In this paper, Raman spectroscopy was applied to the detection of food safety. The determination of carmine in tea drink, o-benzoyl sulfonimide in winter jujube and ethyl maltol in edible oil was studied in order to establish a simple and convenient method. The new method for the detection of bad food additives can further expand the scope of application of Raman spectroscopy and lay a good foundation for the development of Raman spectrum in food safety detection. The main contents and results are as follows: 1. By changing the excitation wavelength and lowering the fluorescence background signal of the sample, three red pigment carmine, rhodamine B and Rhodamine 6G were determined simultaneously. It can distinguish three kinds of substances and can be determined at the same time. By introducing sodium phytate protectant to modify the prepared metal Ag nanoparticles, the method is simple, quick and stable, and the SERS with R6G as probe molecule has good enhancement performance. It can be used to detect o-benzoyl sulfonimide. 3 in winter jujube. Fe3 was introduced as the medium and functional gold nanoparticles were used to detect volatile ethyl maltol. The visual scattering spectrum was used to identify ethyl maltol in food. The method is simple and quick. The results show that the Raman spectroscopy is suitable for the detection of carmine in tea, o-benzoyl sulfonimide in winter jujube and ethyl maltol in edible oil. It shows that Raman spectroscopy as a fast, non-destructive and safe detection technology has a certain application prospect and market potential in food safety detection.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS202.3;O657.37
[Abstract]:The use of food additives has greatly enriched people's material diet culture. However, it is difficult to supervise and control retail bulk food. Illegal merchants abuse additives illegally in food, which not only damages the rights and interests of consumers, but also harms the health of consumers. The results show that rouge, as an azo pigment, can lead to DNA damage induced mutation, and the safety of o-benzoyl sulfonimide as an additive is still controversial. The discovery of ethyl maltol in edible oils means a decrease in the quality and safety of edible oils, which can also lead to symptoms such as headache and vomiting if the edible oils contain ethyl maltol for a long period of time. Perfect sample handling and testing technology can help us to find food safety problems in time. At present, the methods for the determination of different samples are gas chromatography (GC), high performance liquid chromatography (HPLC), mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The operation condition is complex, the instrument is heavy and expensive, but is not suitable for the field rapid analysis and detection. Surface-enhanced Raman spectroscopy (SERS) overcomes the disadvantages of low sensitivity and can provide molecular level information with strong structural characteristics. It plays an important role in the analysis and detection of trace samples. The preparation of SERS substrate which can enhance Raman signal is an important step in the application of surface-enhanced Raman spectroscopy. Gold and silver nanoparticles, among which metal nanoparticles are often used as SERS enhancement substrates due to their inherent surface plasmon resonance effect. Adding a certain amount of protective agent in the process of preparation of nanoparticles can effectively prevent the agglomeration of nanoparticles and improve the stability of nanoparticles. In this paper, Raman spectroscopy was applied to the detection of food safety. The determination of carmine in tea drink, o-benzoyl sulfonimide in winter jujube and ethyl maltol in edible oil was studied in order to establish a simple and convenient method. The new method for the detection of bad food additives can further expand the scope of application of Raman spectroscopy and lay a good foundation for the development of Raman spectrum in food safety detection. The main contents and results are as follows: 1. By changing the excitation wavelength and lowering the fluorescence background signal of the sample, three red pigment carmine, rhodamine B and Rhodamine 6G were determined simultaneously. It can distinguish three kinds of substances and can be determined at the same time. By introducing sodium phytate protectant to modify the prepared metal Ag nanoparticles, the method is simple, quick and stable, and the SERS with R6G as probe molecule has good enhancement performance. It can be used to detect o-benzoyl sulfonimide. 3 in winter jujube. Fe3 was introduced as the medium and functional gold nanoparticles were used to detect volatile ethyl maltol. The visual scattering spectrum was used to identify ethyl maltol in food. The method is simple and quick. The results show that the Raman spectroscopy is suitable for the detection of carmine in tea, o-benzoyl sulfonimide in winter jujube and ethyl maltol in edible oil. It shows that Raman spectroscopy as a fast, non-destructive and safe detection technology has a certain application prospect and market potential in food safety detection.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS202.3;O657.37
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