Approaches for Rapid Determination of the Carcinogen Benzo(a)pyrene and Their Applications in Food and Plastic

多环芳烃（PAHs）是一类分布广泛的致癌性的环境污染物，对人体健康危害极大。苯并(a)芘是目前发现的多种多环芳烃中致癌性最强的，其性质稳定，与其它多环芳烃相关性好，因此常被作为多环芳烃的代表物。食品和塑料制品与人类生活密切相关，因此了解其受苯并(a)芘的污染情况是十分必要的。本论文致力于强致癌物苯并(a)芘的恒能量同步荧光快速检测技术研究。将恒能量同步荧光技术与导数技术及化学计量学方法相结合，建立高灵敏度、高选择性的适用于复杂基体中残留的苯并(a)芘的简便、快速、有效的分析方法。根据食品检测时遇到的导数基线偏离情况，首次提出导数基线校正法。同时将恒能量同步荧光技术应用于塑料制品中两种互为同分异...This dissertation focuses on the studies of analytical methods to rapidly screen benzo(a)pyrene(BaP), one of the most carcinogenic aromatic hydrocarbons (PAHs), in complex matrix by constant-energy synchronous fluorescence spectrometry. Second-derivative constant-energy synchronous fluorescence spectrometry (DCESFS) improves the spectral resolution and selectivity of the fluorescence method. A sim...学位：理学博士院系专业：化学化工学院化学系_分析化学学号：B20042501

低温恒能量同步荧光法同时快速检测食品中多种多环芳烃

恒能量同步荧光法应用于多环芳烃的检测可以提高选择性,低温可使谱带呈指纹特征,提供常温光谱无法获得的光谱细节信息,有助于实现对复杂基体中多环芳烃的检测。文章结合恒能量同步荧光扫描技术与斯波斯基低温技术,建立了食品中多种多环芳烃的低温恒能量同步荧光同时快速分析方法。对低油脂样品直接用正辛烷浸泡,高油脂样品也只需要增加皂化萃取,即可进行光谱扫描来检测食品样中的多种多环芳烃。对两种类型的实际样进行加标回收实验,回收率为80.2%～98.9%,定量工作曲线线性较好(r≥0.9938)。该方法选择性好、操作简便快捷、费用低廉

Rapid Determination of Benzo(a)pyrene in Seafood by Second-derivative Constant-energy Synchronous Fluorescence Spectrometry

海产品中的多环芳烃主要来自于水体污染,而苯并(A)芘是公认的多环芳烃指标,本文针对海产品中的苯并(A)芘含量的检测,建立了简单快速的海产品中的苯并(A)芘含量的二阶导数恒能量同步荧光检测法。海产品样品经过微波辅助皂化萃取后,正己烷萃取液被旋蒸干,后再溶解于二氯甲烷溶液中,以二阶导数恒能量同步荧光光谱法检测,设定恒能量差为1400 CM-1,扫描范围为300~500 nM,对其中的苯并(A)芘进行快速检测,根据海产品样品的谱图特性,用负峰-基线法读荧光强度值,连续标准加入法进行定量分析,整个光谱扫描所需时间只需1 MIn。对实际样品检测回收率在80.5%~118.2%之间,检测限为0.10μg/kg,定量限为0.34μg/kg,线性范围为0.34~250μg/kg。对海产品样品的荧光检测结果与HPlC-fl检测结果基本一致,对有证多环芳烃标准物质的检测结果与参考值一致。Polycyclic aromatic hydrocarbons(PAHs) in seafood samples were ascribed to water pollution,while benzo(a)pyrene was recognized as an indicator of PAHs.A simple and rapid analytical method was developed by combining microwave-assisted pretreatment with second-derivative constant-energy synchronous fluorescence scanning technique for the determination of the benzo(a)pyrene content in seafood samples.The samples were firstly processed with microwave pretreatment,and the extractions were vaporized and redissolved into dichloromethane for further detection.According to the specific spectral properties of seafood samples,peak-to-derivative baseline measurement was used to read the fluorescence data,and standard addition method was applied to the quantitative analysis of seafood samples.The whole spectroscopic scan cost only 1 min.The recoveries ranged from 80.5% to 118.2% for seafood samples and the detection limit was 0.10 μg/kg with linear range from 0.34 to 250 μg/kg.The results obtained with this method were in consistence with those of HPLC-FL method.The satisfactory results acquired by using this method to analyze a certified reference material with a relative error of 7.1% from the certified benzo(a)pyrene concentration.国家自然科学基金资助项目(21375111;21127005); 教育部博士点基金(20110121110011

Determination of Benzo(α)pyrene in Food with Microwave-Assisted Extraction

微波具有萃取效率高、加热均匀、节省时间等特点,而恒能量同步荧光法应用于多环芳烃的检测可提高选择性,导数技术又能放大窄带灵敏度,抑制宽带,改善分辨能力。本文结合恒能量同步荧光扫描技术与导数技术,采用家用微波炉,建立了食品中苯并(α)芘(bAP)的微波辅助萃取-二阶导数恒能量同步荧光法。探讨了影响微波萃取效率的主要因素,如萃取溶剂的类型及使用量、微波萃取时间及冷却时间、微波辐射功率等,并与超声萃取做了比较。对低脂肪样品直接用混合溶剂微波萃取即可进行光谱扫描检测食品中的bAP;对高脂肪样品将皂化和微波辅助萃取这两步操作同时进行,简化操作步骤,缩短样品的前处理时间,使样品的整个分析过程可在1H内完成。该方法操作简单、快速、费用低廉,已应用于实际样检测,低脂肪样品的加标回收率为90.0%~105.0%,高脂肪样品的为83.3%~94.6%,方法重现性好,结果令人满意。Coupling derivative technique and constant-energy synchronous fluorescence scanning technique,a method of determining benzo[α]pyrene in foods by second derivative constant-energy synchronous spectrofluorimetry after microwave-assisted treatment of samples was established using domestic microwave oven.The main factors of influencing the efficiency of microwave extraction were discussed,including the extraction solvent types and amounts,the microwave extraction time,microwave radiation power and cooling time.And the comparison with ultrasonic extraction was made.Low-fat food samples,which were just microwave-extracted with mixed-solvents,could be analyzed immediately by the spectrofluorimetric technique.For high-fat food samples,microwave-assisted saponification and extraction were made at the same time,thus simplifying operation steps and reducing sample analysis time.So the whole sample analysis process could be completed within one hour.This method was simple, rapid and inexpensive.In consequence,it was applied to determine benzo(α)pyrene in food with good reproducibility and the recoveries of benzo(α)pyrene ranged from 90.0%to 105.0%for the low fat samples and 83.3%to 94.6%for high-fat samples.国家自然科学基金项目(21127005;20975084); 福建省科技重点项目(2009Y0046)资

Determination of Benzo[a]Pyrene in Vegetables and Grain Products by Derivative Synchronous Fluorescence Spectroscopy

结合导数恒能量同步荧光扫描技术,采用标准加入法定量检测,导数基线校正法处理数据,建立了一种蔬菜及谷物制品中苯并（α）芘的荧光快速检测方法。一般样品仅需简单超声萃取,深色蔬菜及在370 nm左右有干扰峰的谷物制品也只需增加微波皂化步骤,即可进行光谱扫描。对实际样品高（10μg/kg）、中（5.0μg/kg）、低（1.0μg/kg）浓度的加标回收率在84.2%~103.2%之间,方法重现性好,各类样品的检出限为0.17~0.55μg/kg,标准加入法工作曲线线性范围为0.034~50μg/L。该方法样品前处理简单,无需复杂的纯化分离步骤,适用于蔬菜及谷物制品中苯并（α）芘的快速分析测定。Coupling derivative constant-energy synchronous fluorescence scanning technique with standard addition method and derivative baseline correction for data procession, a rapid and sensitive quantitative detection method for benzo[ α ]pyrene in vegetables and grain products was established. Simple uhrasnnic extraction was the only pretreatment procedure for general samples, and the dark vegetable and grain samples which had interference peak at 370 nm should be pre-processed with saponification before the analysis. It was applied to determine benzo[ α]pyrene in vegetables and grain products with good reproducibility and the recoveries of different spiking concentrations （10, 5.0, 1.0 μ g/kg） ranged from 84.2%-103.2%. The limits of detection were between 0.17-0.55 μ g/kgwith linear range from 0.034-50 IX g/L. This method was simple, rapid, inexpensive and accurate without complex purification separation steps. It was suitable to the rapid determination of benzo[ α ]pyrene in vegetables and grain products.福建省科技重点项目（2009Y0046）,复杂基体干扰食品中强致癌苯并芘快速筛查技术;福建省卫生厅青年科研课题（2015-2-56）

Simultaneous Determination of PAHs in Food by Low-Temperature Constant-Energy Synchronous Fluorescence Spectrometry

The authors developed a rapid analytical method that could determine the PAHs in food samples simultaneously by the coupled approach of Shpol' skii spectroscopy and constant-energy synchronous fluorescence, scanning technique. Low-fat food samples, which were just extracted with octane and high-fat food samples pre-processed with saponification and extracting, could be analyzed immediately. The recoveries ranged from 80.2% to 98.9% and the correlation coefficients of the linearity were higher than 0. 993 8. This method was selective, simple, rapid and inexpensive

Determination of Migration Level of Benzo(a) Pyrene from Paper Cups into Food Simulants

作者简介:林丽容,女,1985年生，厦门大学化学化工学院研究生　　E-mail:[email protected] ＊通讯联系人　　e-mail:[email protected][中文摘要]采用具有高分辨、高灵敏度的导数-恒能量同步荧光法分析测定了不同条件下,纸杯中残留苯并(a)芘在水性模拟液和脂肪模拟液中的迁移量。探讨了模拟物的种类、浸泡时间和温度对纸杯中苯并(a)芘的相对迁移率的影响。结果表明:该分析方法的回收率为89.2%～104.3%;纸杯中残留苯并(a)芘在脂肪模拟液中的相对迁移率明显高于水性模拟液的,纸杯盛装冷水时无苯并(a)芘浸出,而用于盛装热水可浸出苯并(a)芘;温度越高,浸泡时间越长,纸杯中苯并(a)芘向食品模拟液的相对迁移率也越大。[英文摘要]This paper quantitatively determined the migration level of benzo(a)pyrene(BaP) from paper cups into aqueous food simulants or fatty stimulants,under different conditions by second derivative constant-energy synchronous fluorescence spectrometry(DCESFS),which proved to be a method with high sensitivity and spectral resolution.The influences of food simulants,time and temperature on the relative migration percent(%) of benzo(a) pyrene were discussed.Results showed that the recoveries of this method ranged from 89.2% to 104.3%．The migration percent (%) of fatty stimulants was higher than that of aqueous simulants.migration into hot water was also observed,while the migration into cool water was almost negligible.The relative migration percent(%) increased with the increase of time and temperature.国家自然科学基金项目(20975084);福建省科技重点项目(2009Y0046);厦门市卫生局科技计划项目(3502Z20077072)资