Colloids and Surfaces A: Physicochemical and Engineering Aspects, cilt.676, 2023 (SCI-Expanded)
Monodisperse-porous SiO2 microspheres carrying phenylboronic acid linked-flexible polycationic molecular brushes (SiO2@PEI-FPBA MS) was synthesized as a teamed boronate affinity (TBA) sorbent. The combination of enhanced porous properties of selected solid support with a multifunctional, macromolecular spacer arm allowed the synthesis of a superior boronate affinity sorbent (BAS) for batch and continous column chromatography. The sorbent was obtained by covalent binding of 4-formylphenylboronic acid (FPBA) to the polycationic macromolecular spacer-arm, polyethyleneimine (PEI) bound to SiO2 MS 6.3 µm in size. Molecular boronate affinity team on the sorbent was obtained for the first time, by the complex formation between phenylboronic acid (PBA) groups of bound FPBA and remaining primary amine groups of spacer-arm (i.e. branched PEI), by controlling the FPBA feed concentration. SiO2@PEI-FPBA MS obtained by lowering FPBA feed concentration exhibited high binding capacities for cis-diol functionalized biomolecules under neutral conditions as a typical behavior observed with previously produced TBA sorbents. FPBA content, pore volume and specific surface area of the sorbent were determined as 160.4 mg/g, 0.92 cc/g and 141.7 m2/g, respectively. The formation of a TBA complex by intermolecular B-N coordination on SiO2 MS was shown by X-ray photoelectron spectroscopy. The selection of PEI as a macromolecular, multifunctional spacer arm significantly enhanced either the cis-diol adsorption capacity by increasing FPBA content of the sorbent and also by forming a TBA complex with PBA groups. The selected cis-diol carrying agents and glycoproteins, β-nicotinamide adenine dinucleotide, ovalbumin (OVA) and transferrin (TRF) were isolated with the equilibrium adsorptions up to 149 mg/g sorbent and quantitative desorption yields. The comparison of cis-diol binding capacities of SiO2@PEI-FPBA MS obtained at neutral pH with the current TBA sorbents showed that the synthesis of a PEI-assisted TBA sorbent does not involve to include an external complexation agent in the synthesis. High glycoprotein binding capacities under neutral conditions can be obtained only by adjusting the FPBA content of a PEI assisted-TBA sorbent during the synthesis. A boronate affinity micro-chromatography system constructed by packing of SiO2@PEI-FPBA MS into a silica capillary (300 µm i.d.) was also successfully evaluated for the isolation of OVA with different flow rates.