至少要有一个必须是立体化学相互作用，才能形成稳定性不同的非对映体分子络合物，从而达到手性分离的目的。手性固定相的手性识别能力，主要取决于固定相与手性化合物两个对映体之间相互作用力的差别，通常情况下差别越大，往往也越有利于手性分离。在手性液相色谱中，根据固定相或手性选择体的不同，其与对映体之间的相互作用主要包括：π-π电荷转移相互作用、包结络合作用、偶极-偶极吸引作用、氢键相互作用和立体契合作用等。此外，由于采用的手性分离方法、分离模式、手性固定相或手性试剂及色谱条件不同，有可能通过各种不同类型的分子间相互作用而达到手性识别[31]。
在已报道的多糖衍生物手性固定相中，大多是用含不同取代基的苯基异氰酸酯修饰纤维素或直链淀粉后制备成手性固定相。对于这类手性固定相，异氰酸酯中苯环上取代基的位置、种类和数量都是决定CSP手性分离性能的关键因素：苯环上含有卤素等吸电子基团时，能分散氨基氮原子上的孤对电子，使氨基酸性增强[32]，苯环上含烃基等供电子基团则能增加羰基中氧原子的电子云密度。这些都能增强手性选择体形成氢键的能力，有利于以氢键作用为主的手性识别。此外，研究还发现，多糖衍生物中缔合的酰胺越多，高分子的高级结构越规整，越有利于手性分离[33]。因此，在设计手性选择体的结构时，往往需要综合考虑。
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