纺织品中双酚A的表面等离子体共振辅助检测方法

鉴于双酚Ａ（BPA）能够干扰生物的内分泌功能,引起各种生殖异常,威胁着婴幼儿的健康,甚至有致癌的危险等生物危害性,采用表面等离子体共振技术（SPR）对BPA 进行定性定量检测。从传感芯片的修饰、BPA-BSA溶液最佳质量浓度的确定、不同质量浓度BPA的响应情况以及纺织品中BPA的萃取等4个方面出发,探索了SPR技术检测纺织品中BPA的实用性。结果表明,BPA的SPR检测法具有检测速度快、对样品要求低、检测针对性强、检测灵敏度高等优点,适合检测领域的广泛应用,可应用于纺织品中双酚A含量的测定。     

双酚A完全抗原的制备

采用重氮化法在双酚A(BPA)上引入羧基,将其与牛血清白蛋白(BSA)偶联,制备双酚A完全抗原BPAH-BSA.紫外扫描光谱和红外光谱实验表明偶联成功,为进一步制备抗BPA抗体提供了良好的免疫原.     

双酚A在离子液体修饰碳糊电极上的电化学行为及测定

制备1-氰乙基-3-甲基咪唑六氟磷酸盐离子液体修饰碳糊电极,研究双酚A（bisphenol A,BPA）在离子液体修饰碳糊电极上的电化学行为。结果表明,在0.1 mol/L B-R缓冲液（pH 10.0）中,BPA在0.415 V处产生一良好的氧化峰,具有明显的电催化增敏作用。BPA的氧化过程为伴随有质子转移的表面吸附控制的不可逆过程,其电极反应速率为0.32/s。建立了示差脉冲伏安法测定痕量BPA的方法,线性范围为3.0×10－7～6.0×10－5 mol/L,检出限为5.0×10－8 mol/L（RSN=3）。并将其用于奶瓶样品中迁移BPA的测定,结果表明该传感方法为直接电化学检测BPA提供了一种新的思路。     

双酚A的酶联免疫检测方法的建立

将双酚A(BPA)半抗原与牛血清白蛋白(BSA)共价偶联后,制备兔抗双酚A多克隆抗体,建立了双酚A间接竞争酶联免疫(icELISA)检测方法,并对其进行了方法学评价。结果表明:最佳的抗体稀释度为1∶1600,双酚A竞争标准曲线在0.3～100μg·mL-1之间具有良好的线性关系,最低检测浓度为0.001μg·mL-1,重现性实验变异系数均小于10%。交叉反应实验中,与双酚酸和双酚B的交叉反应率分别为20.0%和10.0%;与双酚E和4-枯基苯酚的交叉反应率均在5%以下。水样的添加回收实验,回收率范围为92.5%～107.7%。     

表面增强拉曼光谱快速检测食品中双酚A的研究进展

准确、快速地检测双酚A(BPA)是减少食品中BPA污染的重要环节。表面增强拉曼光谱（SERS）技术作为一种新型的快速检测技术,具有无损、准确、快速、图谱指纹特征强等优点,在食品中BPA快速检测方面具有巨大潜力。本文介绍了SERS的机制及SERS技术在食品中BPA快速检测方面的应用,主要综述了不同SERS基底快速检测BPA的研究进展,以期为BPA的快速检测提供理论支撑。     

基于ZIF-8/Au@f-CNF增敏型双酚A电化学传感器的构建及性能研究

摘 要：目的 设计制备了金属有机框架ZIF-8掺杂、负载金纳米粒子的碳纳米纤维复合材料（ZIF-8-doped gold nanoparticles-loaded carbon nanofibers, ZIF-8/Au@f-CNF），用于玻碳电极（glassy carbon electrode, GCE)表面功能化修饰，以构建食品中双酚A污染物的增敏型电化学传感，并探索对双酚A的增敏检测机制。方法 将利用室温溶剂法制备的ZIF-8与原位还原法制备的负载金纳米粒子的碳纳米纤维（gold nanoparticles-loaded carbon nanofibers, Au@f-CNF）超声混合，滴注在GCE电极表面，构建ZIF-8/Au@f-CNF电化学传感器。运用X-射线光电子能谱仪（X-ray Photoelectron Spectroscopy, XPS）和透射电子显微镜（transmission electron microscopy, TEM）、循环伏安法（cyclic voltammetry, CV）和电化学阻抗法（electrochemical impedance spectroscopy, EIS）对材料表面形貌和电化学性能进行表征，考察了扫速和pH值等参数对双酚A电化学传感行为的影响。结果 ZIF-8/Au@f-CNF复合材料显示较为均匀的掺杂状态，经ZIF-8/Au@f-CN修饰后的GCE电极（ZIF-8/Au@f-CNF/GCE）电活性面积明显提升，是未经修饰裸GCE面积的1.62倍，对双酚A的氧化峰电流峰值显著提升至原来的2.84倍。结论 将ZIF-8的多孔特性和Au@f-CNF的电催化性能相结合，赋予ZIF-8/Au@f-CNF/GCE对目标物良好的吸附性能和电化学反应活性，基于纳米材料的协同效应可实现对双酚A的增敏传感检测，该研究为新型复合材料的开发及增敏传感器构建提供了研究思路和方法借鉴。     

基于上转换纳米粒子与金纳米粒子构建荧光共振能量转移体系检测双酚A方法研究

制备了粒径为13nm的金纳米粒子,在其表面修饰双酚A(BPA)适配体作为能量受体探针;并利用聚丙烯酸(PAA)包覆油溶性的上转换荧光纳米材料(UCNPs)制备水溶性的UCNPs,在其表面修饰适配体互补链形成功能化UCNPs作为能量供体,构建了基于FRET原理的BPA生物传感检测平台。结果表明:该检测体系在1×10~(-9)～1×10~(-3) mol/L时具有良好的线性关系(R~2=0.992 3),检出限低至1×10~(-10) mol/L。     

氯霉素全抗原的合成与鉴定

目的：为获得较高偶联率氯霉素全抗原,探索和优化碳二亚胺法(EDC)合成氯霉素(CAP)与牛血清白蛋白(BSA)全抗原合成条件。方法：采用单因素设计,优化影响合成的主要因素：蛋白浓度、CAP 与BSA 的摩尔比例、反应体系pH 值,通过紫外法和三硝基苯磺酸(TNBS)法测定合成后的偶联率。 结果：EDC 法合成氯霉素抗原较优条件为BSA 浓度15mg/ml、CAP:BSA=70:1、pH7.4,可得到偶联率为15 左右的氯霉素全抗原。结论：EDC法可用于制备较高偶联率的氯霉素全抗原,以用来进行抗体制备。     

非共价作用石墨烯-金纳米复合材料修饰电极的制备及检测双酚A的方法研究

基于阳离子-π非共价作用力制备石墨烯-金纳米复合材料(graphene-AuNPs),研究基于该纳米复合材料修饰玻碳电极建立电化学传感定量检测水样中双酚A的方法。采用扫描电镜(SEM),EDS能谱和X-射线衍射(XRD)技术对该复合材料进行表征,同时制备基于纳米材料修饰的玻碳电极(graphene-AuNPs/GCE),研究双酚A在修饰电极表面的电化学行为,并将该传感器应用于实际样品中双酚A含量的检测。结果表明,所制备的复合材料结构稳定,分散无团聚现象,粒子尺寸大小均匀;所修饰的纳米材料电极对双酚A有明显的电催化性能,双酚A在修饰电极上的电流响应是裸玻电极的6.3倍。在优化条件下,双酚A在浓度为5.7~570 ng/m L和570~2280 ng/m L范围内与氧化峰电流呈线性,检测限为1.9 ng/m L(S/N=3)。将该修饰电极应用于水体样品中双酚A的检测,回收率在78.91~115.54%。     

基于表面印迹技术的双酚A磁性分子印迹聚合物的制备、表征及应用

目的 制备双酚A（bisphenol A, BPA）磁性分子印迹聚合物（magnetic molecularly imprinted polymer, MMIPs）并研究其吸附性能和在奶粉检测中的应用。方法 以双酚A为模板分子,以3-氨丙基三乙氧基硅烷（APTES）为功能单体,采用反向微乳法和表面印迹技术制备了核壳型SiO2包裹Fe3O4 磁性分子印迹聚合物（Fe3O4@SiO2 MMIPs）,并对其进行透射电镜、扫描电镜、傅里叶变换红外光谱、X射线衍射、热重分析和振动样品磁强计表征,并研究Fe3O4@SiO2 MMIPs的吸附性能和在奶粉检测中的应用。结果 制备出的双酚A磁性分子印迹聚合物选择性好,吸附性能好,结合高效液相色谱法,成功应用于奶粉中双酚A的检测。双酚A在5~200 μg/kg 范围内呈现良好的线性关系, 定量限为1.67 μg/kg,回收率为89.9%~92.3%,日内、日间精密度均小于4.0%。结论 Fe3O4@SiO2 MMIPs是一种较好的双酚A富集材料,可用于奶粉中双酚A检测的前处理工艺。     

Estrogenic activity of impurities in industrial grade bisphenol A

The estrogenicities of 10 compounds found as impurities in industrial grade bisphenol A (BPA) were measured by yeasttwo-hybrid assays incorporating the human estrogen receptor alpha(hERalpha) orthe medaka fish (Oryziaslatipes) estrogen receptor alpha (medERalpha). Five impurities showed greater activity than BPA itself in an agonist assay for hERalpha. p-Cumylphenol, the most active of the impurities in the hERalpha assay, was 12 times as active as BPA. The REC10 (10% relative effective concentration: 10% of the activity of 10(-8)M 17,B-estradiol) was 710 nM. Five impurities showed greater activity than BPA in an agonist assay for medERa: 4,4'-(1,3-dimethylbutylidene) bisphenol and 2-(4'-hydroxy-phenyl)-2,4,4-trimethylchroman were nearly equipotent and 9 times as active as BPA, and the REC10 values of these compounds in the medERalpha assay were 280 and 320 nM, respectively. Comparison of the experimentally determined estrogenicities of mixtures of BPA and 4,4'-(1,3-dimeth-ylbutylidene) bisphenol and those calculated by the concentrations addition (CA) method confirmed the suitability of the method for the prediction of the estrogenicities of the mixtures of BPA and its phenolic analogues. The measured estrogenicities of four samples of industrial grade BPA and laboratory grade (pure) BPA were not significantly different in either the hERalpha assay or the medERalpha assay (p > 0.05 in each case). We conclude that the impurities in industrial grade BPA, although some are of much higher estrogenic activity than BPA itself, do not significantly increase the estrogenicity of the industrial compound and therefore do not increase possible adverse health effects from such activity.     

电化学分析法测定食品包装材料中双酚A 的检测

利用功能化单壁碳纳米管(SWCNT)修饰电极大的有效面积和较多的催化活性中心,研究双酚A(BPA)在该修饰电极上的电催化作用。结果表明：在pH6.5 的磷酸盐缓冲溶液(PBS)中,于0.2V 富集100s 后,以扫描速度0.10V/s 进行循环伏安测定,BPA的氧化峰电流(Ipa)与其浓度在2.0 × 10-8～3.5 × 10-5mol/L 范围内呈良好的线性关系,检出限为8.0 × 10-9mol/L(RSN=3)。在进一步考察该修饰电极的稳定性、重现性和干扰实验的基础上,应用于食品包装材料中BPA 含量的测定,回收率在97.5%～105% 之间,结果令人满意。     

Sensitive determination of bisphenol A and bisphenol F in canned food using a solid-phase microextraction fibre coated with single-walled carbon nanotubes before GC/MS

A reliable and sensitive method for simultaneous determination of bisphenol A (BPA) and bisphenol F (BPF) in canned food by gas chromatography-mass spectrometry (GC/MS) is described after extraction and pre-concentration by a new solid-phase microextraction (SPME) adsorbent. The potential of single-walled carbon nanotubes (SWCNTs) as SPME adsorbent for the pre-concentration of environmental contaminants has been investigated in recent years. This work was carried out to investigate the feasibility of SWCNTs as a headspace SPME adsorbent for the determination of bisphenol derivatives in canned food. Potential factors affecting the extraction efficiency, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity were optimized. Calibration curves were linear (r ²≥ 0.994) over the concentration range from 0.30 to 60 µg kg^?1. For both target analytes, the limit of detection (LOD) at signal-to-noise (S/N) ratio of 3 was 0.10 µg kg^?1. In addition, a comparative study between the SWCNT and a commercial polydimethylsiloxane (PDMS) SPME fibre for the determination of bisphenol derivatives in canned food was conducted. SWCNT fibre showed higher extraction capacity, better thermal stability (over 350°C) and longer life span (over 150 times) than the commercial PDMS fibre. The method was successfully applied to determine BPA in canned food samples which were purchased from local markets. BPA was found in some of the samples within the concentration range from 0.5 to 5.2 µg kg^?1.     

免疫亲和柱净化-高效液相色谱法检测两种饮料中双酚A含量

建立了免疫亲和柱净化-高效液相色谱荧光检测法(IAC-HPLC-FL)检测豆奶及橙汁饮料中的双酚A含量。采用甲醇提取、离心、磷酸缓冲溶液稀释后,经免疫亲和柱纯化,用1 mL甲醇-水(80:20,体积/体积)洗脱,应用高效液相色谱法检测。以C₁₈柱为分离色谱柱,甲醇-水(60:40,v/v)溶液为流动相洗脱,流速0.4 mL/min,柱温30℃,进样量10 μL,荧光检测器检测,激发波长228 nm,发射波长310 nm。结果表明:在1.0~300.0 ng/mL的浓度范围内,双酚A的浓度与峰面积呈良好的线性关系(相关系数R2=0.9998),检出限定为1 ng/mL。平均回收率为82.5%~104.6%,相对标准差为2.3%~6.4%。分别选取玻璃瓶装和塑料瓶装的豆奶和橙汁饮料进行双酚A含量检测,玻璃瓶装的豆奶和橙汁饮料中双酚A含量均小于检出限1 ng/mL,而某款塑料瓶装的豆奶和橙汁饮料检测出极其微量的双酚A,其双酚A含量分别为1.44、1.57 ng/mL,处于可接受水平。该方法简单快速、灵敏度高、重复性好,能够有效地分离和检测饮料中的双酚A,适用于豆奶和橙汁等饮料中的双酚A的测定。     

Development and Validation of a LC-FD Method for the Simultaneous Determination of Eight Bisphenols in Soft Drinks

Bisphenol A (BPA) is a chemical widely used as a monomer in the production of polymers of plastics. It acts as an endocrine-disrupting agent and thus its contaminations of food and beverage should be carefully monitored in order to assess consumers’ risk. In this study, we propose a liquid chromatography-fluorescence detection (LC-FD)-validated method for the simultaneous determination of BPA and seven analogues, i.e., bisphenol AF, bisphenol B, bisphenol E, bisphenol F, BPA diglycidyl ether, bisphenol F diglycidyl ether, and Bisphenol M in soft drinks. A one-step solid-phase extraction (SPE) was effective at reducing the interferences, obtaining good purification of the samples, and consequently good recoveries of all analytes. The separation was obtained on a C18 column by using acetonitrile/water 55:45 (v/v) under isocratic conditions. Method validation was performed according to the European Commission Decision 2002/657/EC criteria, providing good results regarding the analytical parameters of linearity, selectivity, sensitivity, precision, recovery, decision limit (CCα), detection capability (CCβ), limit of detection (LOD), limit of quantification (LOQ), stability, and robustness. The method allows the detection of BPA and BADGE at levels much lower than their legal limits in the food, which are 0.06 and 9.00 mg kg^?1, respectively.     

Determination of bisphenol A in wine by sol-gel immunoaffinity chromatography, HPLC and fluorescence detection.

The paper presents a highly selective analytical method for the determination of traces of bisphenol A (BPA) in wine and the results of a survey 59 wine samples sourced from vats (steel, wood and plastic), glass bottles and Tetra briks. The procedure consists of sample clean-up by sol-gel immunoaffinity chromatography followed by determination of BPA by high-performance liquid chromatography and fluorescence detection. The method has a limit of detection (LOD) (S/N = 3) of 0.1 ng ml-1 and a limit of quantitation (LOQ) (S/N = 6) of 0.2 ng ml-1. In 13 of 59 wine samples, the BPA concentration was below the LOQ. The mean and median for all wine samples with BPA concentrations above the LOQ were 0.58 and 0.40 ng ml-1, respectively. These values - the first set of data on BPA in wine - are far lower than previously published BPA levels derived from migration experiments using wine simulants. Experiments carried out by submerging plastic stoppers in ethanol-water (11 : 89, v/v) up to 11 weeks indicated that detectable amounts of BPA can be leached from some stoppers.     

金属食品罐内涂层中双酚类物质的迁移及检测研究进展

鉴于双酚A及其他双酚类物质作为食品罐内涂层材料有潜在的毒性与危害,中国、欧盟、美国等国家均已严格限制它们在金属食品罐内涂料中的使用。本文介绍双酚A、双酚A二缩水甘油醚、双酚F、双酚F二缩水甘油醚的结构、应用、危害、检测方法及迁移结果,并简述固相萃取在样品前处理中的应用。     

食品包装材料中双酚A的研究进展

双酚A是一种内分泌干扰物,会导致人和动物生殖系统、神经系统、免疫系统等的异常。文章综述双酚A的毒性、食品包装材料中双酚A的迁移、食品及食品包装中双酚A检测的提取、分离及检测方法。