Reversed-phase liquid chromatography (RPLC) based octanol-water partition coefficient (logP) or distribution coefficient (logD) determination methods were revisited and assessed comprehensively. Classic isocratic and some gradient RPLC methods were conducted and evaluated for neutral, weak acid and basic compounds. Different lipophilicity indexes in logP or logD determination were discussed in detail, including the retention factor logk_w corresponding to neat water as mobile phase extrapolated via linear solvent strength (LSS) model from isocratic runs and calculated with software from gradient runs, the chromatographic hydrophobicity index (CHI), apparent gradient capacity factor (k_g’) and gradient retention time (t_g). Among the lipophilicity indexes discussed, logk_w from whether isocratic or gradient elution methods best correlated with logP or logD. Therefore logk_w is recommended as the preferred lipophilicity index for logP or logD determination. logk_w easily calculated from methanol gradient runs might be the main candidate to replace logk_w calculated from classic isocratic run as the ideal lipophilicity index. These revisited RPLC methods were not applicable for strongly ionized compounds that are hardly ion-suppressed. A previously reported imperfect ion-pair RPLC method was attempted and further explored for studying distribution coefficients (logD) of sulfonic acids that totally ionized in the mobile phase. Notably, experimental logD values of sulfonic acids were given for the first time. The IP-RPLC method provided a distinct way to explore logD values of ionized compounds.

回顾和评估了基于反相液相色谱（RPLC）的辛醇-水分配系数（logP）或分布系数（logD）测定方法。进行了经典的等度和梯度RPLC方法，并对中性，弱酸和碱性化合物进行了评估。详细讨论了logP或logD测定中的不同亲脂性指标，包括对应于纯水的保留因子logk _w，该纯水是通过等度运行通过线性溶剂强度（LSS）模型外推并通过梯度运行的软件计算出的流动相，色谱疏水性指数（CHI），表观梯度容量因子（k _g '）和梯度保留时间（t _g）。在讨论的亲脂性指标中，等度洗脱或梯度洗脱方法的logk _w与logP或logD最佳相关。因此，推荐logk _w作为logP或logD测定的优选亲脂性指数。从甲醇梯度运行中容易计算出的logk _w可能是替代logk _w的主要候选对象由经典等度运行计算得出的理想亲脂性指数。这些重新审视的RPLC方法不适用于几乎不受离子抑制的强电离化合物。尝试了先前报道的不完善的离子对RPLC方法，并对其进行了进一步探索，以研究在流动相中完全电离的磺酸的分配系数（logD）。值得注意的是，首次给出了磺酸的实验logD值。IP-RPLC方法提供了一种探索电离化合物的logD值的独特方法。