Development of Hyphenated Analytical Instruments for Speciation analysis for Trace Elements

新制备了各种类型的聚甲基丙烯酸酯基整体毛细管柱，用于开发微高效液相色谱- icp - ms和CEC-ICP-MS等联用仪器。采用甲基丙烯酸甘油酯（GMA）和二甲基丙烯酸乙酯在250 μm-i.d的溶液中自由基聚合的方法，建立了强阳离子交换整体毛细管柱进行离子色谱。1 M Na_2SO_3对环氧化物开环的熔融石英毛细管及其后续磺化反应。通过Na^+、NH_4^+、K^+、Mg^<2+>和Ca^<2+>等常见阳离子评价色谱柱的色谱性能。例如，在容量为0.15 mequiv/mL的15 cm柱上，在1 mm/s的法向线速度下（流速为3 μL/min），柱压降约为1 MPa，阳离子的理论板数在3000板/15 cm以上，可以很好地分离阳离子。此外，该柱可以承受至少10毫米/秒的高线速度。这种基于gma的方法被扩展到制备强阴离子交换柱，其中季铵基团通过环氧化物与烷基胺化合物的开环反应引入，然后与苯或烷基卤化物反应。用不同的甲基丙烯酸烷基酯和二甲基丙烯酸乙二醇酯自由基聚合制备了反相色谱柱。此外，该方法还开发了显示反相分离模式的CEC色谱柱。

Various types of polymethacrylate-based monolithic capillary columns were newly prepared for the development of hyphenated instruments such as micro-HPLC-ICP-MS and CEC-ICP-MS. Strong cation-exchange monolithic capillary columns were constructed for ion chromotography by radical polymerization of glycidyl methacrylate (GMA) and ethylene dimethacrylate in a 250-μm-i.d. fused silica capillary and its subsequent sulfonatiori based on ring opening of epoxides with 1 M Na_2SO_3. The chromotographic performance of the columns was evaluated through common cations such as Na^+,NH_4^+,K^+,Mg^<2+> and Ca^<2+>. For an example, they could be well separated from one another on a 15 cm column with a capacity of 0.15 mequiv/mL where the pressure drop of this 15 cm column was ca. 1 MPa at a normal linear velocity of 1 mm/s (a flow rate of 3 μL/min) and the number of theoretical plates for the cations was above 3000 plates/15 cm. Moreover, this column could withstand high linear velocities of at least 10 mm/s. This GMA-based approach was extended to the preparation of strong anion-exchange columns where quaternary ammonium groups were introduced by the ring opening reaction of the epoxides with alkylamine compounds followed by the reaction with benzyl or alkyl halides. Reversed-phase columns were also prepared by radical polymerization of various alkyl methacrylates and ethylene glycol dimethacrylate. Moreover, CEC columns which show reversed-phase separation modes were also developed with this GMA-based approach.