The separation and analysis of complex monosaccharide mixtures is highly challenging and requires typically carefully selected derivatization procedures to avoid changes in the sample composition. Here we present in a comparative study several single- and two-step derivatization approaches for LC and GC separations using a set of reference compounds ranging from C1 building block such as formaldehyde to C6 monosaccharides. Separation conditions have been optimized resulting in the simultaneous separation of 15 unbranched aldoses. By parallel derivatization using hydroxylamine hydrochloride (HACl)/ N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and O-ethylhydroxylamine hydrochloride (EtOx)/ N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and comparative GC measurements we developed a protocol for the unambiguous identification and separation of aldoses, ketoses, alditols and aldonic acids, which commonly occur in complex sugar mixtures as reaction by-products or decomposition products. In particular this procedure helps to deconvolute overlapping analytes and facilitates quantification. Additionally, the method presented here has been investigated in regard to storage life, detection limits, quantification and MS analysis. The broad applicability of this method to different sample matrices is shown for the analysis of food samples and complex aldol reaction mixtures in the formose reaction, which is of great relevance in the context of the origin of life.

复杂的单糖混合物的分离和分析具有很高的挑战性，通常需要精心选择的衍生化程序，以避免样品组成发生变化。在这里，我们在一项比较研究中介绍了使用一组参考化合物（包括甲醛等C1单糖和C6单糖）的一组参考化合物进行LC和GC分离的几种单步和两步衍生化方法。优化了分离条件，可同时分离15个直链醛糖。通过使用盐酸羟胺（HACL）/并行衍生N，O二（三甲基硅烷基）三氟乙酰胺（BSTFA）和Ô -ethylhydroxylamine盐酸盐（ETOX）/ N，O-双（三甲基甲硅烷基）三氟乙酰胺（BSTFA）和比较性GC测量方法，我们开发了用于明确鉴定和分离醛糖，酮糖，醛糖醇和醛糖酸的规程，醛糖，酮糖，醛糖醇和醛糖酸通常作为反应副产物或分解产物出现在复杂的糖混合物中。特别地，该程序有助于对重叠的分析物进行去卷积，并有助于定量。此外，还针对存储寿命，检测限，定量和MS分析对此处介绍的方法进行了研究。显示了该方法对不同样品基质的广泛适用性，用于分析福寿糖反应中的食品样品和复杂的羟醛反应混合物，这在生命起源方面具有重要意义。