Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, Dr. Moliner 50, 46100 Burjassot, Spain.
J Chromatogr A. 2013 Jun 28;1296:140-56. doi: 10.1016/j.chroma.2013.04.027. Epub 2013 Apr 17.
The derivatization reactions commonly used to enhance the analytical signal in the HPLC and CE determination of compounds with hydroxyl functional groups are revised. Focus is placed on the determination of compounds having aliphatic alcohols and phenols while lacking other reactive functional groups. The derivatization with acyl chlorides, organic anhydrides, isocyanates and a variety of other approaches, including oxidation of primary and secondary alcohols, sulfonation, esterification with carboxylic acids, and the use of azides, sulfonyl chlorides and other reagents having miscellaneous leaving groups, is covered. Reactions mainly addressed to introduce a chromophore or a fluorophore in the analyte molecule, or to introduce a charge to enhance sensitivity in MS detection, or to enable CE separation are included. Applications related to the industrial quality control of raw materials and manufactured products, and to the evaluation of their environmental impact are emphasized. The problem of the different response factors of the derivatives when complex mixtures of oligomers are derivatized, as occurs with non-ionic surfactants (mainly fatty alcohol ethoxylates) and soluble synthetic polymers, is discussed. Other applications related to the biochemical, biomedical, pharmaceutical, nutritional and toxicological fields are also reviewed. The reactions, the criteria to be applied to select the reagent, and the characteristics of the derivatives in relation to separation and detection, are discussed.
修订了常用于增强具有羟基官能团的化合物在 HPLC 和 CE 分析中分析信号的衍生化反应。重点放在确定具有脂肪醇和酚类而缺乏其他反应性官能团的化合物上。涵盖了酰氯、有机酐、异氰酸酯和各种其他方法的衍生化，包括伯醇和仲醇的氧化、磺化、与羧酸的酯化以及使用带有各种离去基团的叠氮化物、磺酰氯和其他试剂。包括主要旨在在分析物分子中引入生色团或荧光团、引入电荷以提高 MS 检测灵敏度或实现 CE 分离的反应。强调与原材料和成品的工业质量控制以及对其环境影响的评估有关的应用。讨论了在衍生化复杂的低聚物混合物时，衍生物的不同响应因子的问题，如非离子表面活性剂（主要是脂肪醇乙氧基化物）和可溶性合成聚合物。还回顾了与生化、生物医学、制药、营养和毒理学领域有关的其他应用。讨论了反应、选择试剂时要应用的标准以及衍生物在分离和检测方面的特性。
