Selective cleavage of the polyphosphoester in crosslinked copper based nanogels: enhanced antibacterial performance through controlled release of copper

Polymeric architectures with controlled and well-defined structural features are required to render a sustainable antibacterial surface - a key requirement in the design of polymeric membranes for water purification. Herein, surface selective crosslinking of copper oxide-polyphosphoester (CuO-PPE) hybrid nanogels on to polyvinylidene fluoride-styrene maleic anhydride (PVDF/SMA) ultrafiltration membranes was developed. The hybrid nanogels, composed of PPE and CuO, with inherent antifouling and antibacterial properties, were crosslinked using a macroinitiator (polyethylene glycol, PEG) and subsequently grafted on to PVDF/SMA by alkyne-anhydride reaction. Partially hydrolysed SMA solubilizes membrane proteins and the phosphatase/phospholipase triggers the cleavage of PPE segments resulting in controlled release of Cu ions. This unique strategy renders the membrane surface antibacterial through sustained and controlled release of Cu ions thereby generating intracellular reactive oxygen species (ROS). In addition, the enhanced antibiofouling performance of these membranes is facilitated by the presence of the hydrophilic macroinitiator (PEG and PPE). The modified membranes designed in this study are durable and possess long-term stability due to strong covalent interaction between CuO-PPE and the PVDF/SMA membrane. Studies on the flux, porosity and protein adsorption of the membranes were performed. An enhanced flux recovery ratio was observed for the modified membrane due to the pendant PPE groups (from CuO-PPE) which prohibit irreversible protein adsorption on the PVDF surface. The cytotoxicity of CuO-PPE is greatly reduced because of an effective coverage of CuO by biocompatible PPEs. This study opens up new avenues of fabricating ``smart'' inorganic nanoparticles that can be confined in a soft hybrid polymeric gel network with controlled release of Cu ions thereby precluding ubiquitous bacterial treatment in water filtration systems