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The molecules of mass less than 500 Da are chosen according to selected structural classes in which they give ESI signals primarily as [M+H]<jats:sup>+<\/jats:sup> ions although other ions such as [M\u2212H]<jats:sup>\u2212<\/jats:sup>, [M+Na]<jats:sup>+<\/jats:sup> and [M+NH<jats:sub>4<\/jats:sub>]<jats:sup>+<\/jats:sup> are also reported. The structural classes are drugs with amine\u2010containing side chains, drugs with <jats:italic>N<\/jats:italic>\u2010containing saturated ring structures, 1,4\u2010benzodiazepines, carbohydrates, benzimidazoles, other heterocycles, sulphonylureas, anthracyclines, sulphonamides, penicillins, cephalosporins, tetracyclines, nitrocatechols, steroids, flavonoids, oxazaphosphorines, cannabinols, and miscellaneous molecules. Details are given on the fragmentations, where available, that these ionic species exhibit in\u2010source and in ion\u2010trap, triple quadrupole and time\u2010of\u2010flight mass spectrometers. The review then gives a critical evaluation of these recent HPLC\u2010ESI\u2010MS and CE\u2010ESI\u2010MS analytical methods for the detection and determination of small molecules of clinical and forensic significance. Analytical information on, for example, sample concentration techniques, HPLC and CE separation conditions, recoveries from biological media and limits of detection (LODs) are provided.<\/jats:p>","DOI":"10.1002\/elps.200305850","type":"journal-article","created":{"date-parts":[[2004,6,2]],"date-time":"2004-06-02T05:02:28Z","timestamp":1086152548000},"page":"1413-1446","source":"Crossref","is-referenced-by-count":61,"title":["A critical evaluation of high performance liquid chromatography\u2010electrospray ionisation\u2010mass spectrometry and capillary electrophoresis\u2010 electrospray\u2010mass spectrometry for the detection and determination of small molecules of significance in clinical and forensic science"],"prefix":"10.1002","volume":"25","author":[{"given":"W. 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