Abstract

Chitosan-silica materials offer a specific environment for the adsorption of biofunctional molecules, such as the antimicrobial peptide KR-12. The objective here is to rationalize the changes in the physicochemical properties of these chitosan-silica materials in function of the synthesis pH, using 0.02 w/v % chitosan as catalyst and aggregation agent and, to correlate these characteristics with the loading/delivery and activity/stability of KR-12 antimicrobial peptide. The CS-6 material, prepared at pH 6, exhibits higher surface area (745 m(2)/g) and total pore volume (0.58 cm(3)/g) due to the lower incorporation of chitosan swollen chains (9.36 wt %). Higher pHs produced denser materials (CS-7 and CS-8) with higher entangled chitosan incorporated (> 17 wt%). Adsorption of KR-12 peptide was found to take two different mechanisms depending on the chitosan-silica support, Langmuir-type for CS-6 material and Freundlich-type for CS-7 and CS-8 materials. According to the KR-12 release profiles, more hydrophobic interactions were observed in the CS-6 material exposing Lys and Arg residues from the peptide towards the material surface. This was correlated with the higher antimicrobial activity of this material against S. aureus strain (MIC = 128 mu g/mL). Additionally, the KR-12 peptide adsorbed in the CS-6 hybrid support is 34 % more protected from the proteolytic action of alpha-chymotrypsin than the free one. In conclusion, the proposed models of different porous environments in the studied chitosan-silica materials supports the KR-12 peptide loading/delivery mechanisms, leading to biofunctionalized solid antimicrobial materials exhibiting proteolytic stability. This knowledge is useful for designing new antibacterial materials for biomedical applications. (C) 2019 The Authors. Published by Elsevier B.V.