Abstract

Abstract Fundamentals of multidimensional liquid chromatographic techniques are overviewed, including off‐line, serial, stop‐and‐go, and heart‐cutting and comprehensive separation modes, with attention to resolution, peak capacity, efficiency, orthogonality, and selectivity with special attention to the effects of sample structure on the retention and optimization of two‐dimensional (2‐D) separation systems, including the selection of columns, flow rate, fraction volumes, and mobile phase. Experimental set‐up, modulation of the fraction collection and transfer from the first to the second dimension, compatibility of mobile phases in comprehensive LC × LC, and 2‐D asymmetry are addressed. The survey presents various coupled 2‐D modes (RP × RP, HILIC × RP, IEX × RP, and SEC × RP) and problems with their on‐line coupling.

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