Development of Green Chemistry-oriented Analytical Method for Environmental and Waste Samples by Nano/Micro LC/MS

微液相色谱/质谱法（LC/MS）可以通过节省溶剂和减少浪费来促进绿色化学。然而，微LC/MS对高疏水性化合物，特别是小分子化合物的测定大多无效。我们开发了一种微型LC/MS方法，用于测量具有环境意义的疏水性和小分子质量化合物。该方法包括微型LC中的溶质聚焦技术和质谱中的激发氩电离法。在分析微柱上游的微混合器中，用亲水溶液动态稀释疏水溶液，成功地对高疏水化合物进行了溶质聚焦。以乙醛同质物的O-（4-氰基-2-乙氧基苄基）羟胺（CNET）衍生物为例，当以0.2 ~ 10ppb的浓度注入5uL时，理论极板数在27000 ~ 60000之间。这些化合物的工作曲线基本呈线性，回归良好。受激氩电离对某些疏水化合物是有效的。丁酮产生高信噪比（s/n）的M+离子，其电离能（I.E.）和质子亲和能（PA）分别为9.52eV和827.3kJ/mol。picoline（即：9.26eV, PA: 949.1kJ/mol）产生的M+离子和MH+离子的s/n分别是常压化学电离（APCI）产生的s/n的8倍和30倍。通过本研究，开发了一种节省和减少有机溶剂的方法，有助于环境和废物分析中的绿色化学

Micro liquid chromatography/mass spectrometry (LC/MS) can contribute green chemistry by saving solvent and reducing waste. However micro LC/MS was mostly ineffective for measuring highly hydrophobic compounds, in particular for small molecules. We developed a micro LC/MS method for measuring hydrophobic and small molecular mass compounds of environmental interest. The method includes solute focusing technique in micro LC and an ionization method by excited argon for mass spectrometry.Solute focusing was successfully performed for highly hydrophobic compounds by dynamically diluting hydrophobic solution with hydrophilic solution in micro mixer upstream of analytical micro column. In case of O-(4-cyano-2-ethoxybenzyl) hydroxylamine (CNET) derivatives of aldehyde homologues in acetone, theoretical plate numbers of the peaks were ranged 27, 000to 60, 000 when 5uL of the solution in 0.2to 10ppb were injected. Working curves of those compounds were mostly linear with good regression.Ionization by excited argon was efficient for some hydrophobic compounds. It generated M+'ion with high signal to noise ratio (s/n) from butanone, of which the ionization energy (I.E.) and the proton affinity (PA) are 9.52eV and 827.3kJ/mol, respectively. M+'ion and MH+ ion generated from picoline (I.E.: 9.26eV, PA: 949.1kJ/mol) were respectively 8 and 30 times higher in s/n than those from Atmospheric Pressure Chemical Ionization(APCI).Through this study, a way to save and reduce organic solvents, which contribute green chemistry in environmental and waste analysis, was developed