Hayakawa K, Terai N, Dinning P G, Akutsu K, Iwamoto Y, Etoh R, Murahashi T
Graduate School of Natural Science and Engineering, Kanazawa University, Ishikawa, Japan.
Biomed Chromatogr. 1996 Nov-Dec;10(6):346-50. doi: 10.1002/(SICI)1099-0801(199611)10:6<346::AID-BMC605>3.0.CO;2-Y.
Various metal powders were batch screened as possible on-line reducers for nitropolycyclic aromatic hydrocarbons (NPAHs), in particular 1,3-dinitropyrene (1,3-DNP, 1,8-DNP and 1-nitropyrene (1-NP) and it metabolites. Zinc was found to be an excellent reducer in chemiluminescent compatible mobile phases without any associated disposal problems. Zinc reducer column parameters, namely pH, buffer concentration, packing composition (zinc:glass beads or zinc:silica gel) and column length were all optimized for the HPLC determination system with chemiluminescence detection, named NPAH analyser. The system consisted of three pumps, sample injector, reducer column packed with zinc:glass beads switching valve with a cutting loop, separation column (ODS), chemiluminescence detector and integrator. The mobile phase for the separation column and chemiluminescence reagent solution were respectively acetonitrile:imidazole-HClO44 and acetonitrile containing bis(2,4,6-trichlorophenyl)oxalate and H2O2. When the reducer column was introduced before the separation column, 1,3-, 1,6- 1,8-DNPs and 1-NP in benzene:ethanol extracts from airborne particulates were separately determined with detection limits of 2-50 fmol, respectively, in a 100 microL sample. When the reducer column was introduced just after the separation column, 1-NP, 1-nitrosopyrene and 1-aminopyrene in the incubation mixture of 1-NP and the Salmonella typhimurium YG1021 strain were separately determined with detection limits as low as sub fmol levels. 1,8-DNP and its metabolite were also separately determined in the incubation mixture of 1,8-DNP and the S. typhimurium TA98 strain.
对各种金属粉末进行了分批筛选，以确定其作为硝基多环芳烃（NPAHs），特别是1,3-二硝基芘（1,3-DNP）、1,8-二硝基芘和1-硝基芘（1-NP）及其代谢物的潜在在线还原剂的可能性。结果发现，锌是化学发光兼容流动相中的一种优良还原剂，且不存在任何相关的处置问题。针对配备化学发光检测的高效液相色谱测定系统（称为NPAH分析仪），对锌还原剂柱的参数，即pH值、缓冲液浓度、填料组成（锌：玻璃珠或锌：硅胶）和柱长进行了优化。该系统由三个泵、进样器、填充有锌：玻璃珠的还原剂柱、带切割环的切换阀、分离柱（ODS）、化学发光检测器和积分仪组成。分离柱的流动相和化学发光试剂溶液分别为乙腈：咪唑 - 高氯酸和含有双（2,4,6-三氯苯基）草酸酯和过氧化氢的乙腈。当在分离柱之前引入还原剂柱时，对空气中颗粒物苯：乙醇提取物中的1,3-、1,6-、1,8-DNPs和1-NP进行了分别测定，在100微升样品中的检测限分别为2 - 50飞摩尔。当在分离柱之后立即引入还原剂柱时，对1-NP与鼠伤寒沙门氏菌YG1021菌株的孵育混合物中的1-NP、1-亚硝基芘和1-氨基芘进行了分别测定，检测限低至亚飞摩尔水平。还对1,8-DNP与鼠伤寒沙门氏菌TA98菌株的孵育混合物中的1,8-DNP及其代谢物进行了分别测定。
