Enhanced antimicrobial activity and physicochemical stability of rapid pyro-fabricated silver-kaolinite nanocomposite

Abstract

The present research aims to enhance the antimicrobial activity of kaolinite surfaces by a one-step cost-effective and energy-efficient dry thermal reaction, producing an antibacterial and antifungal silver-kaolinite (Ag-Kao) nanocomposite agent. Pharmaceutical grade kaolin powder samples, with variable kaolinite structural order–disorder degree, were homogeneously mixed with silver nitrate in a proportion 1:4 AgNO:kaolin (w/w) and sintered at 400 °C for 30 min. The composition, microstructure, microtexture and surface characteristics of the pyro-fabricated nanocomposites were characterized by XRD/XRF diffractometry, differential scanning calorimetry DSC, FT-IR spectroscopy, TEM/EDX, zeta potential (mV) measured within the 2–12 pH range, and BET method. Physicochemical stability was evaluated by silver dissociation testing under close-neutral and acidic conditions with Ag content assay using ICP-OES. The resulting Ag-Kao nanocomposites exhibited bulk silver contents ranging from 9.29% to 13.32% with high physicochemical stability in both neutral and acidic mediums (Ag dissociation rate <0.5% in 5 days). Ag nanocrystals exhibited particle sizes ranging from 5 to 30 nm, which were embedded and reinforced within the kaolinite matrix. The sizes of the Ag nanocrystals and their distribution patterns on the edges and faces of kaolinite platelets were controlled by the structural order–disorder degree. Highly ordered kaolinites (Hinckley Index, HI > 1) produced platelet edge-clustered silver nanocrystals due to the abundance of the dangling hydroxyls on platelet edges, while the highly disordered kaolinite (HI < 1) provided homogeneous platelet basal-doped silver nanocrystals due to the presence of some residual charges by exposed basal hydroxyl groups with interplatelet silver diffusivity. At pH 2, the magnitude of the positive surface charge was influenced by the silver nanocrystal size. Nanocomposites with the smallest silver nanocrystals (10–5 nm) exhibited the highest positive zeta potential (+15.2 mV to +17.0 mV), while those with larger silver nanocrystals (up to 30 nm) indicated lower positive zeta potential values (+9.5 mV to +3.6 mV). Under the same testing conditions using the Mueller-Hinton broth microdilution method, the raw kaolin samples did not show any significant antimicrobial activity, while all the pyro-fabricated Ag-Kao nanocomposite samples showed potent antibacterial and antifungal activity at low doses (MIC range 0.1–0.0125 mg/mL). Therefore, modulation of the effective electrostatic surface charge of the kaolinite platelets, via thermal doping of silver within their basal planes and edges, was found to be strongly dependent on the pH as well as the size and microtexture of the silver nanocrystals (mainly controlled by the order–disorder degree HI). The resulting modified nanostructure, with physicochemical stability and the efficient surface properties of the designed pyro-fabricated nanocomposite, led to an enhanced synergistic biophysical antimicrobial activity.