Retention prediction of analytes in reversed-phase high-performance liquid chromatography based on molecular structure

A QSPR Study of the p Solute Polarity Parameter to Estimate Retention in HPLC

“…These included mainly aromatic derivatives such as phenols, anilines, phenones, halobenzenes, nitrobenzenes, alkylbenzenes, and esters and also several aliphatic compounds such as alkanes and alcohols. The p values for 152 compounds were calculated from retention data published by Smith and Burr, which were determined in a Spherisorb ODS-2 (100 × 5 mm) column using several acetonitrile−water mobile phases buffered at pH 7. − For other 63 compounds, p values were calculated from the data published by Hanai and Hubert obtained in ERC-1000 ODS (150 × 6 mm), Develosil ODS-5 (150 × 4.6 mm), or Unisil Q C 18 (150 × 4.1 mm) columns and acetonitrile−water mobile phases − and by Rosés and Bosch in a LiChrospher 100 RP-18 (100 × 5 mm) column, using acetonitrile−water mobile phases too . All these values were transferred to the Smith and Burr chromatographic system by linear regression .…”

“…Therefore, a reference chromatographic system to refer p values obtained in different column/mobile phase arrangements was established . This reference data set was selected from the retention measurements of Smith and Burr in a Spherisorb ODS-2 column and acetonitrile/water mobile phases. − Thus, a wide database of more than 200 compounds of a different nature is now available. , Equation 1 and the described polarity parameters have demonstrated to be able to transfer successfully retention data between solvent systems and between columns …”

RAPID METHOD FOR ESTIMATING OCTANOL-WATER PARTITION COEFFICIENT (LOG POCT) FROM ISOCRATIC RP-HPLC AND A HYDROGEN BOND ACIDITY TERM (A)

“…Analysis using the solvation equation (1) on the set of isocratic retention values on an octyldecyl stationary phase with acetonitrile measured by Smith et al 30 showed excellent correlation with the molecular descriptors, which had previously been carried out before by Abraham et al 31 The results are set out in Table 1. Comparing the coefficients of the solvation equation given in Table 1 and the coefficients of equation 2 for log P oct , it is clear that they are different.…”

“…Our test set was measured on a Luna C 18 stationary phase, which is different to that used by Smith et al 30 from which the equations were derived, and so some slight differences in results might be expected. We recommend that you set up your own equations for equation 4 and 5 on a carefully chosen set of training compounds, because log k values are usually not inter-laboratory comparable.…”

“…Here, log P oct is the equivalent partition value in octanol/water estimated from chromatographic isocratic measurement corrected by the hydrogen bond count (HBC). We also obtain the solvation equations for log k values with methanol organic modifier 33 on the same data set by Smith et al, 30 Table 5. The latter does not account for the dif- Figure 3.…”