采用液相色谱-电化学检测法分离和检测青霉胺与谷胱甘肽的双（烷硫基）硒化物

Separation and detection of bis(alkylthio)selenides of penicillamine and glutathione by liquid chromatography with electrochemical detection.

作者信息

Killa H M, Rabenstein D L

机构信息

Department of Chemistry, University of California, Riverside 92521.

出版信息

J Chromatogr. 1989 Mar 31;465(2):359-68. doi: 10.1016/s0021-9673(01)92673-1.

DOI:10.1016/s0021-9673(01)92673-1

PMID:2745604

Abstract

Sensitive and selective methodology is described for the simultaneous determination of thiols, disulfides and bis(alkylthio)selenides in mixtures formed by reaction of selenious acid with thiols. The methods are based on separation of the various compounds by reversed-phase ion pairing chromatography followed by detection with an electrochemical detector equipped with dual mercury/gold amalgam electrodes in series in the eluent stream. Thiols are detected directly at the downstream electrode. Bis(alkylthio)selenides and disulfides are detected indirectly by first reducing them at the upstream electrode followed by detection of the reduction products at the downstream electrode. Bis(alkylthio)selenides are reduced at less negative potentials than disulfides, making it possible to selectively detect them in mixtures with disulfides. Detector response to bis(penicillamine)selenides is linear from 1.1.10(-7) M up to at least 1.2.10(-4) M; the detection limit is estimated to be less than 2 pmol bis(penicillamine)selenide.

摘要

描述了一种灵敏且具有选择性的方法，用于同时测定亚硒酸与硫醇反应形成的混合物中的硫醇、二硫化物和双（烷硫基）硒化物。这些方法基于通过反相离子对色谱法分离各种化合物，然后使用配备有串联双汞/金汞齐电极的电化学检测器在洗脱液流中进行检测。硫醇在下游电极直接检测。双（烷硫基）硒化物和二硫化物通过首先在上游电极将它们还原，然后在下游电极检测还原产物来间接检测。双（烷硫基）硒化物在比二硫化物更低的负电位下被还原，这使得在与二硫化物的混合物中选择性检测它们成为可能。检测器对双（青霉胺）硒化物的响应在1.1×10⁻⁷ M至至少1.2×10⁻⁴ M范围内呈线性；估计检测限小于2 pmol双（青霉胺）硒化物。