Correlations between the zeta potentials of silica hydride-based stationary phases, analyte retention behaviour and their ionic interaction descriptors

• Zeta potential measurements were used to study key silica hydride properties.
• Origin of the retention behaviour of basic, acidic and neutral analytes investigated.
• Correlation analyses of zeta potential and analyte retention established.
• Linear solvation energy relationship revealed the role of ionic contributions.
• New insights into the retention mechanisms for HILIC and ANPC modes achieved.

In this study, the zeta potentials of type-B silica, bare silica hydride, the so-called Diamond Hydride™ and phenyl substituted silica hydride stationary phases have been measured in aqueous-organic media and correction procedures developed to account for the more negative zeta potential values in media containing different acetonitrile contents. Retention studies of 16 basic, acidic and neutral compounds were also performed with these four stationary phases with mobile phases containing 0.1% (v/v) formic acid and various acetonitrile–water compositions ranging from 0–90% (v/v) acetonitrile. The retention properties of these analytes were correlated to the corrected stationary phase zeta potentials measured under these different mobile phase conditions with R2 values ranging from 0.01 to 1.00, depending on the stationary phase and analyte type. Using linear solvation energy relationships, stationary phase descriptors for each stationary phase have been developed for the different mobile phase conditions. Very high correlations of the zeta potentials with the ionic interaction descriptors were obtained for the type-B silica and the Diamond Hydride™ phases and good correlation with bare silica hydride material whilst there was no correlation observed for the phenyl substituted silica hydride phase. The nature of the retention mechanisms which gives rise to these different observations is discussed. The described methods represent a useful new approach to characterize and assess the retention properties of silica-hydride based chromatographic stationary phases of varying bonded-phase coverage and chemistries, as would be broadly applicable to other types of stationary phase used in the separation sciences.

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