Lignin-based thermoresponsive macromolecules via vitamin-induced metal-free ATRP

Abstract

Abstract An environmentally-friendly process for the modification of lignin with thermoresponsive polymers was employed, providing well-defined structures with narrow molecular weight distribution (Mw/Mn\xa0=\xa01.44). We report a biocompatible vitamin-inspired photoinitiation system composed of two components i.e. riboflavin (vitamin B2) as a photosensitizer and ascorbic acid (vitamin C) as a mild reducing agent. Under blue light LEDs irradiation at 460\xa0nm (5.0\xa0mW\xa0cm−2) the presented two-component photoinitiation setup enables grafting of poly(ethylene glycol) methyl ether methacrylate (OEGMA500) from brominated lignin via metal-free ATRP approach. A series of cyclic voltammetry (CV) measurements were conducted to electrochemically characterize ATRP initiators, both brominated lignin and lignin-based polymers, confirming preserved chain-end functionality of the prepared macromolecules. Received polymers with lignin core and POEGMA side chains exhibited thermoresponsive properties, which were investigated by determination of number average sizes of macromolecules by dynamic light scattering (DLS) and transmittance by ultraviolet/visible (UV-Vis) absorption spectroscopy of KL-g-(POEGMA-Br)10 aqueous solution. The in vitro curcumin release studies showed that the active substance is released from drug-loaded micelles in a thermo-sensitive manner. Prepared lignin-based macromolecules will show wide application as crucial components of thermoresponsive coatings, potentially creating bioactive surfaces characterized by antifouling properties, controlling cell adhesion or used as biosensors, due to PEG-containing side chains in branched polymers.