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Nowadays solid materials in which amino groups are linked to silica matrices through alkyl chains of different length (C18, C8, C4) are successfully employed in CO2 capture and storage technologies, as well as in a variety of chromatographic applications. In particular, their use as stationary phases finds remarkable success in performing HILIC separations and, in general, in the effective resolution of important compound classes (e.g. mixtures of mono- or oligo-saccharides). In this study an original and operationally simple procedure designed to quantify the density of basic groups (typically amino groups) chemically bonded to the surface of porous solids, which also allows a full recovery of the analysed material, is presented. The method is based on the preventive acid-base reaction of the basic groups linked to the solid by 3,5-dinitrobenzoic acid (DNBA). The quantification of the basic functionalities is then performed by an UV-spectrophotometric retro-titration of the thus salified solid matrix (or, alternatively, by HPLC approach), resorting to a preventive either acid or basic displacement of DNBA from the matrix. The uncertainty of the density measurements is assessed by 13%.

Two new chiral and restricted-access materials containing glycopeptide antibiotics as chiral selectors (chiro-Glyco-RAM) were designed, suitable for the direct HPLC injection of biological fluids containing chiral drugs without any sample pre-treatment or pre-columns coupling. The external surface of the porous silica support was covered with a bio-compatible hydrophilic polymeric network (polyvinyl alcohol, PVA) while the chiral phase based on either teicoplanin (TE) or teicoplanin aglycone (TAG) was exclusively confined to the internal region. The chiro-Glyco-RAM supports were synthesized by the following steps: (a) introduction of 3-aminopropyl groups on 100 A pore size silica gel; (b) activation of the aminopropylated silica with 1,6-diisocyanatohexane; (c) functionalization of the external region of the porous silica with PVA; (d) covalent linking of TE/TAG to the internal surface. The average pore diameter of the chiro-Glyco-RAM supports, calculated by inverse size-exclusion chromatography (ISEC), was about 80 A and able to exclude macromolecules heavier than about 20,000 Da (such as the most abundant serum proteins) from the pores. The recovery of bovine serum albumin (BSA) was almost quantitative. HPLC analyses of model chiral drugs were performed using hydro-organic mobile phases consisting of an organic solvent (acetonitrile or methanol) and aqueous solutions of ammonium acetate (0.020 M) or ammonium formate (0.0025-0.0050 M).

An original synthetic method was developed for the preparation of a family of six novel deactivated restricted-access materials (RAMs), belonging to the group of the internal surface reversed-phase (ISRP) supports. The supports (ISRP-RAM phases A–F) have an alkyl-chain (14 methylenes) with two embedded ureido groups bound only to the internal surfaces of the porous silica, and polyvinyl alcoholic groups (PVA, 100 000 → 22 000 molecular weight) chemically bound to the external surfaces. The average pore diameters of the prepared ISRP-RAM supports, calculated by inverse size-exclusion chromatography, ranged between 49 A and 88 A, and were able to exclude macromolecules heavier than about 24 000 Da (such as serum proteins) from the pores. The novel supports were designed for the determination of a semi-synthetic anticancer drug of the camptothecin family in human plasma, but they represent universal ISRP-RAM supports not limited to such class of compounds.