Baeyens W R, Ling B L
Laboratory of Pharmaceutical Chemistry and Drug Analysis, Faculty of Pharmaceutical Sciences, State University of Ghent, Belgium.
J Pharm Biomed Anal. 1989;7(12):1385-94. doi: 10.1016/0731-7085(89)80143-8.
Luminescence emission from drugs is strongly dependent on their physicochemical environment. Several biomedically and environmentally important compounds and pharmaceuticals exhibit sufficient intrinsic luminescence properties to allow their determination by high-performance liquid chromatography (HPLC) with fluorimetric, chemiluminescence or room temperature phosphorimetric detection. In the case of weakly fluorescing compounds it is possible to use the dependence of the emitted radiation on the molecular environment at the moment of measurement. The composition of the eluent, i.e. solvents, added salts and buffers, pH and ionic strength, oxygen content and temperature, are of the highest importance for the luminescence detection of drugs in solution (e.g. in liquid chromatography) or adsorbed onto solid surfaces (e.g. in thin-layer chromatography). Post-column or post-plate acid-base manipulation and the use of specific reagents may remarkably enhance the observed luminescence of several molecules. The term "enhancement" of luminescence comprises various sample treatments leading to an increase of the emitted radiation. These treatments include the addition of non-fluorescent compounds to, or the creation of organized media (surfactants, cyclodextrins, heavy atoms) in, the sample to be measured. They may also involve changes in molecular environment, pH, the application of excessive drying conditions, the removal of oxygen, the protection of adsorbed compounds against non-radiative decay mechanisms by means of specific spraying or dipping conditions, amongst others. The use of organized media in luminescence spectroscopy is growing. Many of the recent studies have involved micelles for enhancing the fluorescence, room temperature phosphorescence and chemiluminescence of several chemicals. Cyclodextrins are increasingly used for various analytical applications. Liquid paraffin, triethanolamine, dodecane, Triton X-100 and Fomblin Y-Vac are commonly used fluorescence enhancers in chromatographic assays. Examples of these systems in drug analysis are presented.
药物的发光发射在很大程度上取决于其物理化学环境。几种对生物医学和环境具有重要意义的化合物及药物表现出足够的固有发光特性,从而可以通过高效液相色谱法(HPLC)结合荧光、化学发光或室温磷光检测来进行测定。对于弱荧光化合物,可以利用测量时发射辐射对分子环境的依赖性。洗脱液的组成,即溶剂、添加的盐和缓冲剂、pH值和离子强度、氧气含量以及温度,对于溶液中(如在液相色谱中)或吸附在固体表面上(如在薄层色谱中)的药物的发光检测至关重要。柱后或板后酸碱处理以及使用特定试剂可以显著增强几种分子的发光。“发光增强”这一术语包括导致发射辐射增加的各种样品处理。这些处理包括向待测样品中添加非荧光化合物,或在其中创建有序介质(表面活性剂、环糊精、重原子)。它们还可能涉及分子环境、pH值的变化,施加过度干燥条件,去除氧气,通过特定的喷雾或浸渍条件保护吸附的化合物免受非辐射衰变机制的影响等。有序介质在发光光谱学中的应用正在不断增加。最近的许多研究都涉及胶束用于增强几种化学物质的荧光、室温磷光和化学发光。环糊精越来越多地用于各种分析应用。液体石蜡、三乙醇胺、十二烷、吐温X - 100和全氟聚醚Y - Vac是色谱分析中常用的荧光增强剂。文中列举了这些系统在药物分析中的实例。