欧盟指令：罐头材料安全计量新标准

从2005年12月31日起，欧盟正式施行三年前发布的指令——〈关于某些环氧衍生物在食品包装中的使用》——欧盟各成员国禁止使用这类食品包装，包括含有BADGE和NOCE等这类物质的食品罐内涂料和食品包装用粘合剂，也禁止含有该类成分的罐头产品进口到欧盟市场。而我国罐头内涂料现在大多采用#214环氧酚醛涂料，其中就含有该欧盟指令禁用的BADGE（双酚A二缩水甘油醚）、和NOGE（线性酚醛清漆缩水甘油醚）。     

氰酸酯/环氧树脂共混物热分解动力学

利用动态TGA方法研究了双酚A二缩水甘油醚环氧树脂和酚醛环氧树脂与双酚A二氰酸酯的两类共混物的热稳定性。用Coats-Redfern研究了不同配比共混物的热分解动力学。结果表明,氰酸酯含量大的双酚A二缩水甘油醚环氧树脂/双酚A二氰酸酯共混物具有两阶段分解机理,而环氧含量大的双酚A二缩水甘油醚环氧树脂/双酚A二氰酸酯共混物具有均一的热分解活化能;相比较而言,酚醛环氧树脂/双酚A二氰酸酯共混物的分解活化能基本上不随温度和组成变化。从后期失重温度和活化能看,酚醛环氧树脂/双酚A二氰酸酯共混物具有比双酚A二缩水甘油醚环氧树脂/双酚A二氰酸酯共混物更高的热稳定性。     

牛奶中抗生素的液相芯片检测方法研究

利用悬液芯片系统建立了一种快速、多成份、高灵敏、高通量的抗生素残留的检测方法.使用表面具有羧基的微球作为固相载体,将人工合成的抗生素全抗原键合到微球上作为捕获抗原,与样品中的抗生素竞争体系中抗生素的单克隆抗体,使用藻红蛋白标记的二抗作为荧光探针,构建间接竞争反应体系.反应体系经悬液芯片系统可对荧光探针进行测定并对包被不同抗原的不同型号微球进行分类识别,实现抗生素的高通量检测.以检测牛奶中头孢氨苄、卡那霉素为例,头孢氨苄、卡那霉素的检测限分别为13.98 ng/mL、23.44 ng/mL,50%抑制的质量浓度(IC50)分别为56.88 ng/mL、190.09 ng/mL.     

采用高效液相色谱法测定PET瓶装饮用水中双酚A及其迁移量

目的建立基于高效液相色谱技术的双酚A分析方法,用于快速准确检测襄阳市售5种PET瓶装饮用水塑料包装中的双酚A含量及其在饮用水中的迁移量。方法样品经前处理后,采用高效液相色谱-紫外检测器方法分离检测,选择ODS-C18色谱柱(4.6 mm×150.0 mm,5μm),流动相为甲醇-乙酸铵溶液(体积比为50∶50),柱温为30℃,流速为1 mL/min,检测波长为280 nm。结果双酚A的检出限为0.004μg/mL,在0.02μg/mL质量浓度条件下的相对标准偏差为4.32%,在线性浓度为0.01～200μg/mL内的检测信号与双酚A浓度具有良好的线性相关性(r20.9999),方法分析性能满足国标限量要求。襄阳市售主要品牌PET瓶装饮用水包装中虽均含有一定量的双酚A,但饮用水中未检出双酚A。PET包装中双酚A在0.4,4,40μg/g等3个加标水平的回收率为70.30%～113.00%,饮用水中双酚A在0.1,1,10μg/g等3个加标水平的回收率为90.00%～119.00%,加标回收结果良好。结论此方法简便、准确、高效,适用于PET瓶装饮用水包装中双酚A含量及迁移量的分析。     

加速溶剂萃取-GC-MS/MS法测定食品接触材料中双酚A、双酚F及其衍生物的残留量

建立了加速溶剂萃取-气相相色谱-串联质谱法测定食品接触材料(婴儿奶瓶)中双酚A、双酚F及其衍生物残留量的分析方法。样品用二氯甲烷作提取剂,用加速溶剂萃取仪进行了提取,经乙酸酐衍生化,用气相色谱-串联质谱仪进行了定性、定量分析。结果表明:BPA,BPF,BADGE,BFDG 4种化合物的回收率范围在78.9%～101.1%之间,相对标准偏差小于10%,线性关系良好,方法的检出限分别为0.2,0.1,5,5 ng/g,该方法简便、快速、灵敏度高、重复性好。     

离子色谱法在饮用水溴酸盐分析中的应用

采用抑制电导离子色谱法(IC)检测饮用水中的痕量溴酸盐.对样品中高浓度的干扰组分氯离子进行了处理,避免其对测定的影响.溴酸盐浓度在5ng/mL～100ng/mL范围内具有良好的线性关系,相关系数为0.9999,方法的定量限为2ng/mL(S/N=10),样品加标回收率大于91.6%.该方法经试验,成功地试用于各种饮用水中溴酸盐含量的测定.     

食品罐内涂膜中有害化学物质的迁移与检测

食品罐内涂膜中有害化学物质主要有双酚A、双酚A二缩水甘油醚、双酚F、双酚F二缩水甘油醚、酚醛清漆甘油醚及其衍生物等,国际上对这些有害化学物质的使用做出了相关限定。常用的食品罐检测前处理方法有液-液萃取法、固相萃取法以及固相微萃取法等,食品罐内涂膜中有害化学物质的检测方法主要有高效液相色谱法、气相色谱-质谱法和酶联免疫法。针对食品罐内涂膜有害物质迁移的研究还存在有害物质毒性机理不健全和检测方法不完善等问题,寻找一种精确、简便且可同时检测多种有害物质的方法,并加强对有害化学物质迁移模型的建立是该领域的研究方向。     

大田软海绵酸荧光偏振免疫分析方法研究

设计使用荧光试剂PDAM与大田软海绵酸单(OA)反应合成了荧光标记物,并在OA单克隆抗体的基础上建立TOA荧光偏振免疫(FPIA)检测方法.该FPIA方法检测限为4.6 ng/mL,检测范围为7.0-88.7 ng/mL.IC(50)为24.9 ng/mL.本方法操作简单、稳定,有望应用于高通量筛查牡蛎样品中OA含量.     

高效液相色谱法测定桶装水及水桶中双酚A含量

该文建立固相萃取/高效液相色谱测定桶装水及水桶中双酚A含量的方法。桶装水样品经C18固相萃取柱富集,水桶用二氯甲烷溶解甲醇提取双酚A;采用C18色谱柱,以乙腈-水(V/V,60:40)为流动相,检测波长224 nm,高效液相色谱法测定双酚A含量。在最优检测条件下,双酚A在0.4～10μg/mL浓度范围内线性关系良好(r2=0.999 8),方法的检出限为0.069μg/mL,定量限为0.23μg/mL,平均回收率为98.3%。该方法简便、灵敏、重现性好,所抽取桶装水中并未检测到双酚A的存在,水桶材质中检测出双酚A的含量为37.1μg/g。     

北京市售桶装饮用水中双酚A的污染水平

目的建立定量分析桶装饮用水中双酚A的方法,研究北京市桶装饮用水中双酚A的污染水平。方法采用固相萃取技术进行样品前处理,运用液相色谱?质谱联用法进行样品检测。结果在质量浓度为122.9~1190.7 ng/L范围内,在最优的质谱检测条件下,一级质谱的线性回归方程为y=69.4x+2186.1,相关系数为0.993,检出限为7.0 ng/L,定量限为23.5 ng/L。方法的回收率为78.8%~108.1%,相对标准偏差(n=6)≤13.5%。在随机检测的北京市6个水站的53种桶装饮用水中有36种检出双酚A,但浓度均低于《生活饮用水卫生标准》(GB 5749—2006)中规定的双酚A限值(0.01 mg/L)。结论该方法选择性好、灵敏度高、重现性好,能够满足定量检测桶装饮用水中双酚A的要求。北京市售桶装水中较为普遍地存在双酚A,长期饮用有健康风险。     

Synthesis and characterization of novel hyperbranched polyimides/attapulgite nanocomposites

Novel hyperbranched polyimides/attapulgite (HBPI/AT) nanocomposites were successfully synthesized by in situ polymerization. HBPI derived from novel 2,4,6-tri[3-(4-aminophenoxy)phenyl]pyridine (TAPP) and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA). 4,4′-diphenylmethane diisocyanate (MDI) modified AT copolymerized with HBPI and the nanocomposites formed multilinked network. Chemical structure, morphology, thermal behavior, and mechanical properties of nanocomposites were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and tensile testing et.al. Results indicated that modified AT was homogeneously dispersed in matrix and resulted in an improvement of thermal stability, mechanical properties and water resistance of HBPI/AT nanocomposites.     

金刚烷基聚砜的合成及性能

采用1,3-二(4-羟苯基)金刚烷(DPAD)与二氟二苯砜(DFDPS)、二氯二苯砜(DCDPS)的溶液缩聚反应合成了1,3-二(4-羟苯基)金刚烷基聚砜(ADPFS,ADPCS);通过DPAD、双酚A(BPA)、DFDPS的溶液缩聚反应合成了金刚烷-双酚A基共聚砜(ADPFAS)。GPC测试结果表明,ADPFS和ADPCS的数均分子量分别为41000和6600,高活性的单体(DFDPS)有利于合成高分子量的聚砜。热分析结果表明,ADPFS与ADPFAS起始热分解温度高于410℃,与PSF起始热分解温度相近,但ADPFS的玻璃转化温度为235℃,ADPFAS的玻璃转化温度为210℃,显著高于商用双酚A型聚砜(PSF)的玻璃转化温度(186℃)。     

Isolation of alpaca anti-hapten heavy chain single domain antibodies for development of sensitive immunoassay

Some unique subclasses of Camelidae antibodies are devoid of the light chain, and the antigen binding site is comprised exclusively of the variable domain of the heavy chain (VHH). Although conventional antibodies dominate current assay development, recombinant VHHs have a high potential as alternative reagents for the next generation of immunoassay. We expressed VHHs from an immunized alpaca and developed a VHH-based immunoassay using 3-phenoxybenzoic acid (3-PBA), a major metabolite of pyrethroid insecticides as a model system. A phage VHH library was constructed, and seven VHH clones were selected by competitive binding with 3-PBA. The best immunoassay developed with one of these VHHs showed an IC(50) of 1.4 ng/mL (limit of detection (LOD) = 0.1 ng/mL). These parameters were further improved by using the phage borne VHH, IC(50) = 0.1 ng/mL and LOD = 0.01 ng/mL. Both assays showed a similar tolerance to methanol and dimethylsulfoxide up to 50% in assay buffer. The assay was highly specific to 3-PBA and its 4-hydroxylated derivative, 4-hydroxy 3-PBA, (150% cross reactivity) with negligible cross reactivity with other tested structural analogues, and the recovery from spiked urine sample ranged from 80 to 112%. In conclusion, a highly specific and sensitive VHH for 3-PBA was developed using sequences from immunized alpaca and phage display technology for antibody selection.     

Assessment of specific binding proteins suitable for the detection of paralytic shellfish poisons using optical biosensor technology

Paralytic shellfish poisoning (PSP) toxin monitoring in shellfish is currently performed using the internationally accredited AOAC mouse bioassay. Due to ethical and performance-related issues associated with this bioassay, the European Commission has recently published directives extending procedures that may be used for official PSP control. The feasibility of using a surface plasmon resonance optical biosensor to detect PSP toxins in shellfish tissue below regulatory levels was examined. Three different PSP toxin protein binders were investigated: a sodium channel receptor (SCR) preparation derived from rat brains, a monoclonal antibody (GT13-A) raised to gonyautoxin 2/3, and a rabbit polyclonal antibody (R895) raised to saxitoxin (STX). Inhibition assay formats were used throughout. Immobilization of STX to the biosensor chip surface was achieved via amino-coupling. Specific binding and inhibition of binding to this surface was achieved using all proteins tested. For STX calibration curves, 0-1000 ng/mL, IC50 values for each binder were as follows: SCR 8.11 ng/mL; GT13-A 5.77 ng/mL; and R895 1.56 ng/mL. Each binder demonstrated a different cross-reactivity profile against a range of STX analogues. R895 delivered a profile that was most likely to detect the widest range of PSP toxins at or below the internationally adopted regulatory limits.     

Molecular characterization of monoclonal antibodies against aflatoxins: a possible explanation for the highest sensitivity

We screened and established seven hybridoma cell lines that secrete anti-aflatoxin monoclonal antibodies with different sensitivities. Among these antibodies, 1C11 exhibited the highest sensitivity against all four major kinds of aflatoxins (AFB1, AFB2, AFG1, and AFG2) (IC(50) 0.0012-0.018 ng mL(-1) in the enzyme linked immunosorbent assay (ELISA) system, visual limit of detection of 0.03-0.25 ng mL(-1)). To better understand the interactions between these antibodies and aflatoxins, as well as to guide their potential sensitivity improvement in recombinant antibodies, we used multiple sequence alignment and molecular modeling combined with molecular docking to clarify the molecular mechanism of the highest sensitivity of 1C11 against aflatoxins. Our results show that hydrogen bond and hydrophobic interaction formed by Ser-H49 and Phe-H103 in the antibody with the hapten played the most important roles in determining the binding affinity. Further experiments performed on antibody mutants, designed on the basis of the computational models, supported the prediction of the interaction mode between the antibody and the hapten. Although the factors that influence antibody sensitivity are highly interdependent, our experimental and modeling studies clearly demonstrate how structural differences influence the binding properties of antibodies against the target hapten with different sensitivities.     

Determination of hydrolysis products of sulfur mustards by reversed-phase microcolumn liquid chromatography coupled on-line with sulfur flame photometric detection and electrospray ionization mass spectrometry using large-volume injections and peak compression

On-line coupling of reversed-phase microcolumn liquid chromatography (micro-RPLC) and sulfur-selective flame photometric detection (S-FPD) was studied for the selective and direct determination of thiodiglycol, bis(2-hydroxyethylthio)methane, 1,2-bis(2-hydroxyethylthio)ethane, 1,3-bis(2-hydroxyethylthio)propane, and 1,4-bis(2-hydroxyethylthio)butane, which are breakdown products of the chemical warfare agents called sulfur mustards. Both isocratic and gradient elution were used. To improve sensitivity, large-volume injections were applied together with peak compression by displacement for late-eluting analytes. With S-FPD, detection limits of 1 microgram/mL were obtained for all compounds. Using the same approach, the target analytes as well as various oxidation products could be identified by micro-RPLC with electrospray ionization mass spectrometry (ESI-MS) and ESI-MS/MS. The optimized micro-RPLC-S-FPD system was successfully used for the analysis of a spiked soil sample.     

增韧双马来酰亚胺的性能及其热稳定性

以二苯甲烷双马来酰亚胺和邻－二烯丙基双酚Ａ为共聚单体，制成了增韧的双马来酰亚胺９ＢＭＩ）树脂，并测定了树脂的各种性能，对影响因素作了探讨。还研究了双马来酰亚胺及ＢＭＩ／二烯丙基双酚Ａ固化树脂的热稳定性，提出了交联产物的热分解历程。     

咪唑封闭水性聚氨酯复鞣剂的制备及表征

通过分子设计,以咪唑为封闭剂,1,6-己二异氰酸酯（HDI）、二羟甲基丙酸（DMPA）、2,2-二（4-羟基苯基）丙烷、聚酯二醇为原料制备出咪唑封闭水性聚氨酯复鞣剂（BPU）。用FT-IR、动态激光光散射（DLS）、TEM、TGA、DSC分别对BPU分子结构、乳胶粒形态及热性能进行了表征,分析了BPU复鞣剂的分子作用基础。结果表明产物分子结构中出现了羧基、咪唑环和聚氨酯结构;乳胶粒呈较为规则的、具有核壳结构的球形,粒径的多分散性是BPU具有良好选择填充性的微观原因。TGA和DSC分析显示BPU耐热性较高并随封闭率增加而略有降低;BPU解封温度范围为107.5～124.5℃,峰值为115.1℃;应用过程中BPU解封程度极低,利于助染性能的提高。     

Apta-biosensors for nonlabeled real time detection of human IgE based on carbon nanotube field effect transistors

In this study, we demonstrated the aptamer-based biosensor (apta-biosensor) using CNT-FET devices for label free detection of allergy diagnosis by IgE detection. In order to detect the IgE, two kinds of receptor (monoclonal IgE antibody and anti-IgE aptamer)-modified CNT-FET devices were fabricated. The binding event of the target IgE onto receptors was detected by monitoring the gating effect caused by the charges of the target proteins. Since the CNT-FET biosensors were used in buffer solution, it was crucial to use small-size receptors like aptamers than whole antibodies so that the charged target IgE could approach the CNT surface within the Debye length distance to give a large gating effect. The results show that CNT-FET biosensors using monoclonal IgE antibody had very low sensitivity (minimum detectable level 1000 ng/mL), while those based on anti-IgE aptamer could detect 50 ng/mL. Moreover, the aptamer-modified CNT-FET herein could successfully block non-target proteins and could selectively detect the target protein in an environment similar to human serum electrolyte. Therefore, aptamer-based CNT-FET devices enable the production of label-free ultrasensitive electronic biosensors to detect clinically important biomarkers for disease diagnosis.