Analytical applications of enhanced drug luminescence

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.