分散液-液微萃取-气相色谱-质谱法同时测定中毒样品中有毒生物碱和鼠药

建立了分散液-液微萃取(Dispersive liquid-liquid micro-extraction,DLLME)与气相色谱-质谱(GCMS)联用同时测定中毒样品中3种鼠药(毒鼠强、溴鼠灵、溴敌隆)和5种有毒生物碱(莨菪碱、东莨菪碱碱、钩吻碱、士的宁、马钱子碱)的方法。100μL萃取剂氯仿与600μL分散剂甲醇混合后,迅速注入样品,萃取过程在乳化体系中完成;以8000 r/min离心5 min,使两相分层,取下层有机相进行GC-MS分析。考察了萃取剂、分散剂的种类和体积、萃取时间、pH值及盐浓度对萃取效率的影响。在优化条件下,各目标物在水样、尿样、黄酒样的检出限为0.003~1.0μg/L,在米饭样品检出限为0.002~0.2μg/kg;各目标物低、中、高加标回收率为81.0%~110%,精密度均小于7%。本方法灵敏度高,快捷高效,适用于中毒样品中有毒生物碱和鼠药的同时测定。     

Ion mobility spectrometric analysis of vaporous chemical warfare agents by the instrument with corona discharge ionization ammonia dopant ambient temperature operation

The ion mobility behavior of nineteen chemical warfare agents (7 nerve gases, 5 blister agents, 2 lachrymators, 2 blood agents, 3 choking agents) and related compounds including simulants (8 agents) and organic solvents (39) was comparably investigated by the ion mobility spectrometry instrument utilizing weak electric field linear drift tube with corona discharge ionization, ammonia doping, purified inner air drift flow circulation operated at ambient temperature and pressure. Three alkyl methylphosphonofluoridates, tabun, and four organophosphorus simulants gave the intense characteristic positive monomer-derived ion peaks and small dimer-derived ion peaks, and the later ion peaks were increased with the vapor concentrations. VX, RVX and tabun gave both characteristic positive monomer-derived ions and degradation product ions. Nitrogen mustards gave the intense characteristic positive ion peaks, and in addition distinctive negative ion peak appeared from HN3. Mustard gas, lewisite 1, o-chlorobenzylidenemalononitrile and 2-mercaptoethanol gave the characteristic negative ion peaks. Methylphosphonyl difluoride, 2-chloroacetophenone and 1,4-thioxane gave the characteristic ion peaks both in the positive and negative ion mode. 2-Chloroethylethylsulfide and allylisothiocyanate gave weak ion peaks. The marker ion peaks derived from two blood agents and three choking agents were very close to the reactant ion peak in negative ion mode and the respective reduced ion mobility was fluctuated. The reduced ion mobility of the CWA monomer-derived peaks were positively correlated with molecular masses among structurally similar agents such as G-type nerve gases and organophosphorus simulants; V-type nerve gases and nitrogen mustards. The slope values of the calibration plots of the peak heights of the characteristic marker ions versus the vapor concentrations are related to the detection sensitivity, and within chemical warfare agents examined the slope values for sarin, soman, tabun and nitrogen mustards were higher. Some CWA simulants and organic solvents gave the ion peaks eluting at the similar positions of the CWAs, resulting in false positive alarms.     

氧瓶-离子色谱法测定树脂中的卤素和硫元素

含有卤素和硫元素的树脂样品经氧瓶法燃烧分解，用含H2O2的去离子水溶液吸收，离子色谱法分离测定．本法简便、快速，特别适于测定树脂中不活泼的卤族元素，且可同时测定。CI、S的相对标准偏差分别为0．22%,0．36％，最大绝对误差分别为0．43％和0．80％。树脂中CI、S的含量在0．28mmol/g～14mmol／g内可用此法准确测定，其最低检测限为0．05mmol／g。     

一种检测麻痹性贝毒的高效液相色谱法

提出了一种利用高效液相色谱法同时分析麻痹性贝毒GTX组分和NEO/dcSTX/STX组分的方法。本法仅使用了一种缓冲溶液作为流动相,在InertsilC8-3色谱柱(250mm×4.6mm,5μm)上,采用梯度改变乙腈在流动相中的比例和流速,一次进样可同时定性及定量待测试样中的上述全部毒素组分。该缓冲溶液为9.0mmol/L磷酸铵缓冲溶液(pH=7.2),含有2.8mmol/L的庚烷磺酸钠。色谱分离过程首先以纯水相缓冲溶液进行等度洗脱,在16.5~19min向流动相中梯度加入1.5%的乙腈,加速GTX3和GCX2的洗脱,以避免GTX2的色谱峰与乙腈的溶剂峰重叠,随后从19min开始加大流动相中乙腈的比例为8.5%,以缩短边缘组分的保留时间。荧光检测器的激发波长和发射波长分别设为330nm和390nm。用本方法分析染毒的华贵栉孔扇贝和近江牡蛎,证实了本方法对PSP毒素具有良好的分析测定效果。     

高效液相色谱法测定灭鼠毒饵中溴敌隆

采用紫外检测器波长为265mm，Cl8不锈钢柱，丙酮为溶剂萃取样品中的有效成分，对灭鼠毒饵中的溴敌隆进行了测定。回收率为97．5％-100．6％，相对标准偏差为1．5％-3．6％。