Spheres-on-sphere (SOS) silica particles are prepared in a one-pot scalable synthesis from mercaptopropyltrimethoxysilane with hydrophilic polymer and cationic surfactant under alkaline conditions. The SOS particles exhibit solid-core porous-shell properties. The fast separation of small molecules and proteins with low back pressure are demonstrated by high-performance liquid chromatography (HPLC) for the columns packed with SOS-particles.

A new chiral stationary phase for ultrahigh-pressure liquid chromatography (UHPLC) applications was prepared by covalent attachment of the Whelk-O1 selector to spherical, high-surface-area 1.7-μm porous silica particles. Columns of varying dimensions (lengths of 50, 75, 100, and 150 mm and internal diameters of 3.0 or 4.6 mm) were packed and characterized in terms of permeability, efficiency, retention, and enantioselectivity, using both organic and water-rich mobile phases. A conventional HPLC Whelk-O1 column based on 5.0-μm porous silica particles and packed in a 250 mm × 4.6 mm column was used as a reference. Van Deemter curves, generated with low-molecular-weight solutes on a 100 mm × 4.6 mm column packed with the 1.7-μm particles, showed H(min) (μm) and μ(opt) (mm/s) values of 4.10 and 5.22 under normal-phase and 3.74 and 4.34 under reversed-phase elution conditions. The flat C term of the van Deemter curves observed with the 1.7-μm particles allowed the use of higher-than-optimal flow rates without significant efficiency loss. Kinetic plots constructed from van Deemter data confirmed the ability of the column packed with the 1.7-μm particles to afford subminute separations with good efficiency and its superior performances in the high-speed regime, compared to the column packed with 5.0-μm particles. Resolutions in the time scale of seconds were obtained using a 50-mm-long column in the normal phase or polar organic mode. The intrinsic kinetic performances of 1.7-μm silica particles are retained in the Whelk-O1 chiral stationary phase, clearly demonstrating the potentials of enantioselective UHPLC in terms of high speed, throughput, and resolution.

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Porous silica microspheres have wide applications in various areas. It has been a challenge to produce uniform silica microspheres with tunable pore size. In this study, uniform porous silica microspheres were synthesized using a modified Sto ¨ber method. Cetyltrimethylammonium bromide (CTAB) was used as a cationic surfactant to introduce ordered mesoporosity into silica spheres. Hydrophilic polymers poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), and poly(ethylene glycol) (PEG) were introduced into the reaction system. It was found that the use of PVA led to the formation of uniform and well-dispersed porous silica microspheres. The effect of the polymers on pore size and particles morphology was also studied. Another cationic surfactant dihexadecyldimethylammonium bromide (DiCTAB) and a nonionic surfactant (Brij-35) were further investigated by replacing CTAB. Uniform nonporous silica nanospheres were formed for Brij-35 and Brij-35/PVA systems. The use of DiCTAB resulted in submicrometer silica spheres with high surface area and larger pore size. The addition of PVA into the reaction system dramatically reduced the surface area and pore volume. The mesopores in the silica microspheres formed from the CTAB-PVA template were expanded using 1,3,5-trimethylbenzene and N,N-dimethyldecylamine as swelling agents by a hydrothermal method. The pore size was increased from 2.7 to 4.5 nm and 6.5 nm, respectively.