Electrospray Ionization Mass Spectrometry for the Quantification of Inorganic Cations and Anions
Electrospray Ionization Mass Spectrometry for the Quantification of Inorganic Cations and Anions
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DOI：
10.2116/analsci.31.7
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发表时间：
2015-01
影响因子：
1.6
通讯作者：
H. Hotta;K. Tsunoda
中科院分区：
文献类型：
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作者：
H. Hotta;K. Tsunoda
综述了本实验室近年来在电喷雾电离质谱仪(ESI-MS)上对无机阳离子和阴离子进行定量的研究进展。在向样品溶液中加入过量的氨基多羧酸盐(APC)试剂后，ESI-MS以负离子模式将金属离子测定为氨基多羧酸盐(APC)络合物的单价负离子。在所研究的APC中，我们发现反式-1，2-二氨基环己烷-N，N，N‘，N’-四乙酸(CyDTA，络合物的化学形态表示为H_n Cydta^n−4)是最好的螯合剂。用尺寸排除柱在线分离样品中的金属-APC络合物和基质盐。用该方法成功地测定了生物标准物质(CRM)、橄榄叶(BCR-062)、浮游生物(BCR-414)和土壤标准物质(JSAC-0401)中铝、镍、铜、锌、铅的总量。根据金属、络合剂和被分析物阴离子三元络合物的形成，用电喷雾质谱联用法测定了卤离子(X^−=F^−、Cl^−、Br^−和I^−)和氰化物(CN^−)。测定了13族元素氮三乙酸(Nta，Hn Nta^n−3)和卤化物[AlF(Nta)]^−(F^−)和[Inx(Nta)]^−的三元络合物的负离子，其检出限分别为：F^−为10nmoldm^−3，Cl^μ为0.31nmoldm^−3，Br^−为3.8nmoldm^−3，I^−为1.6nmoldm^−3。以CN？−为例，通过测定Cu^II、CN？−和4-(2-吡啶偶氮)间苯二酚(PAR，H_n PAR^n−2)的三元络合物，即[^63Cu^II(CN)(PAR)]^−(m/z302)，得到了20nmoldm^−3.此外，还建立了电喷雾质谱(ESI-MS)定量测定六价铬和三价铬的方法，其中六价铬的测定采用HCrO4-−(m/z117)，三价铬的测定采用[Cr^-III(Cydta)]-−。
Recent studies from our laboratory on electrospray ionization mass spectrometry (ESI-MS) for the quantification of inorganic cations and anions are reviewed. Metal ions were determined by ESI-MS in negative-ion mode as monovalent negative ions of their aminopolycarboxylate (APC) complexes, where excess amounts of the APC agents were added to sample solutions. Among the APCs studied, we found trans-1,2-diaminocyclohexane- N , N , N ′, N ′-tetraacetic acid (CyDTA, the chemical forms in a complex were expressed as H_ n cydta^ n −4) as the best chelating agent. A size exclusion column was used for on-line separation of the metal-APC complexes from matrix salts in samples. Total amounts of Al, Ni, Cu, Zn, and Pb in the biological certified reference materials (CRM), Olive Leaves (BCR-062) and Plankton (BCR-414), and in a soil CRM (JSAC-0401) were successfully determined by the proposed method. Halide ions (X^− = F^−, Cl^−, Br^− and I^−) and cyanide (CN^−) were determined by ESI-MS based on the formation of ternary complexes of metals, chelating agents and the analyte anions. Negative ions of the ternary complexes of group 13 elements, nitrilotriacetic acid (NTA, H_ n nta^ n −3), and halides, i.e. , [AlF(nta)]^− for F^−, and [InX(nta)]^− for other halides, were measured; the limits of detection (LODs) were 10 nmol dm^−3 for F^−, 0.31 μmol dm^−3 for Cl^−, 3.8 nmol dm^−3 for Br^−, and 1.6 nmol dm^−3 for I^−, respectively. In the case of CN^−, an LOD of 20 nmol dm^−3 was obtained based on measurements of the ternary complex of Cu^II, CN^− and 4-(2-pyridylazo)resorcinol (PAR, H_ n par^ n −2), i.e. , [^63Cu^II(CN)(par)]^− ( m / z 302). Moreover, quantitative methods for Cr^VI and Cr^III by ESI-MS were developed, where HCrO_4^− ( m / z 117) for Cr^VI and [Cr^III(cydta)]^− for Cr^III were used for measurements.