基于硼亲和分子印迹策略的MOF/MIPs对沙丁胺醇的选择性吸附和计算模拟

为了探索所构筑的硼酸功能化金属有机框架(MOF)表面印迹材料(FSU-BA@MIP)对底物的亲和识别能力,对FSU-BA@MIP的金属-有机骨架材料(UiO-66-BA)中的3-羧基苯硼酸配体与沙丁胺醇间的硼亲和作用进行计算,再采用密度泛函理论(DFT)对FSU-BA@MIP材料对沙丁胺醇的选择性机理进行模拟,最后进行选择性实验.计算结果表明,离子化的3-羧基苯硼酸与沙丁胺醇间存在的氢键作用使得这两种物质有较强的作用力,更容易形成硼酸环酯;与竞争物质相比, UiO-66-BA与沙丁胺醇的结合能与反应能最低,说明所形成的FSU-BA@MIP印迹材料对底物沙丁胺醇具有特异性吸附.分析结果与实验得到的沙丁胺醇的最高吸附量一致,说明UiO-66-BA是一种可用于分析顺式二醇化合物的理想硼酸功能化材料.     

Simultaneous determination of eleven amphenicols and antiviral drugs in aquatic products by ultra-high performance liquid chromatography-tandem mass spectrometry coupled with PRIME HLB solid phase extractionEI北大核心CSCD

An efficient ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was established for the simultaneous determination of 11 amphenicols and antiviral drugs in aquatic products including fish, shrimp, soft-shell turtle and shellfish samples. Each sample was dispersed with 4%(w/w)sodium chloride solution, and extracted with 2%(V/V) ammonia-ethyl acetate solution. After the concentration of the extract, the residue was redissolved in 0.2%(V/V) aqueous solution of formic acid-acetonitrile (20∶80, V∶V), purified with Oasis PRIME HLB cartridge, and detected by UPLC-MS/MS. The samples were analyzed directly on the ZORBAX RRHD Eclipse Plus C18 column using 5 mmol/L ammonium formate and acetonitrile as mobile phase. The quantitative determination of the analytes was carried out under the multiple reaction monitoring mode with positive and negative electrospray ionization using internal standard method. Results showed that there were good linear relationships for all analytes in the corresponding concentration ranges, with the correlation coefficients not less than 0.996. The limits of quantification ranged from 0.2 to 2.0 µg/kg. The average spiked recoveries were between 84.6% and 110% with the relative standard deviations of 1.0% to 14%. The method, which has been used in risk monitoring, is suitable for rapid determination of amphenicols and antiviral drugs in aquatic products. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

通过型固相萃取-液相色谱-串联质谱法同时快速测定鱼肉中7种微囊藻毒素

采用通过型固相萃取净化去除样品基质中脂类物质的干扰,建立了鱼肉中7种微囊藻毒素的液相色谱-串联质谱快速分析方法。样品经80℃水浴热处理后用体积分数为90%的甲醇水溶液进行提取,使用Oasis PRiME HLB通过型固相萃取柱净化。净化后的样品采用Waters XSelect HSS T3色谱柱分离,以0.1%(体积分数)甲酸乙腈溶液和0.1%(体积分数)甲酸水溶液为流动相,梯度洗脱,多反应监测正离子模式扫描,采用基质匹配溶液外标法定量。研究了7种微囊藻毒素的质谱离子化特征,结果表明,酸能显著增加双电荷离子的响应强度。7种目标物在相关范围内线性关系良好,相关系数不低于0.99,定量限为0.30~2.0μg/kg,基质加标回收率为70.6%~96.1%,相对标准偏差为3.4%~9.6%。该方法前处理操作简便,灵敏度和准确度高,可实现鱼肉中多种微囊藻毒素的同时快速测定。     

超高效液相色谱-四极杆-飞行时间质谱法快速筛查和确证渔药中86种非法添加化学品

建立了超高效液相色谱-四极杆-飞行时间质谱法快速筛查与确证渔药中86种非法添加禁限用药物的方法。渔药以80%(v/v)乙腈水溶液进行提取,通过稀释降低基质效应,采用ACQUITY PREMIER HSS T3色谱柱进行分离,以甲醇和0.1%甲酸水溶液作为流动相进行梯度洗脱,采用电喷雾双喷离子源(Dual AJS ESI)正离子模式分析检测。建立了86种药物的一级精确质量数据库和二级碎片质谱库。在全扫描采集模式下,以化合物的色谱保留时间、精确质量数、同位素分布和同位素丰度比定性;在Target MS/MS采集模式下,通过二级碎片离子的匹配进一步确证化合物,以准分子离子峰的峰面积定量,实现渔药样品中多目标药物的快速定性定量分析。86种药物在各自的线性范围内均呈现良好的线性关系,相关系数均大于0.99,中草药制剂和抗生素粉剂的定量限(LOQ)范围分别为1~15 mg/kg和5~75 mg/kg,添加回收率范围为76.8%~112.1%,相对标准偏差(RSD, n=3)小于11.7%。该方法快速、简便、准确、灵敏,适用于不同种类渔药中禁限用非法添加药物的高通量筛查。将该方法应用于浙江省渔用投入品质量安全监督抽检项目中,共筛查60个样品,其中8种中草药制剂筛查出说明书中未明确标明的药物成分,1种抗生素粉剂未检出有效成分。该研究为渔药的质量安全监控提供了有效的技术手段。