Quantitative structure-chromatographic retention relationship study of six underivatized equine estrogens.

Underivatized estrone (ES), equilin (EQ), equilenin (EQN) and their corresponding 17 alpha-diols 17 alpha-estradiol (ESD), 17 alpha-dihydroequilin (DHEQ) and 17 alpha-dihydroequilenin (DHEQN) were separated by TLC, RP-HPLC and capillary GC. Their dipole moments (mu) and Randić's connectivity indices ((1)chi) were determined as parameters of importance for the separation. The number of H atoms was taken as an additive structural parameter of importance for the quantitative structure-chromatographic retention relationship study (QSRR). Principal component analysis (PCA) was applied in order to find similarities and dissimilarities between 9 TLC and 10 RP-HPLC systems. PCA indicated that proton donor-proton acceptor interactions play the most important role for the TLC and RP-HPLC separation. The two-dimensional non-linear map of PC variables showed that the keto-estrogens (ES, EQ and EQN) and the corresponding diols (ESD, DHEQ and DHEQN) form two separate clusters. The relationship between GC retention of equine estrogens characterized by Kováts indices (KI), their (1)chi and mu was expressed by the equation KI/100 = al(1)chi+ b/mu(2) + c. The biological activity of the estrogens was related to log 1/mu(2).