Facile Surface Modification with Croconaine-Functionalized Polymer on Polypropylene for Antifouling and NIR-Light-Mediated Photothermal Sterilization.

Biomedical-device-associated infection (BAI) is undoubtedly a major concern and a serious challenge in modern medicine. Therefore, the development of biomedical materials that are capable of resisting or killing bacteria is of great importance. In this work, a croconaine-functionalized polymer with antifouling and near-infrared (NIR) photothermal bactericidal properties was prepared and facilely modified on polypropylene (PP) to combat medical device infections. Croconaine dye is elaborately modified as a "living" initiator, termed CR-4EBiB, for preparing amphiphilic block polymers by atom transfer radical polymerization (ATRP). In the formed polymer coating, the hydrophobic block can strongly adhere to the surface of the PP substrate, whereas the hydrophilic block is located on the outer layer by solvent-induced resistance to bacterial adhesion. Under the irradiation of an NIR laser (808 nm), the croconaine dye in the coating achieved maximum conversion of light to heat to effectively kill E. coli, S. aureus, and methicillin-resistant Staphylococcus aureus (MRSA). This work provides a facile and promising strategy for the development of implantable antibacterial biomedical materials.

NIR-Photocontrolled Aqueous RAFT Polymerization with Polymerizable Water-Soluble Zinc Phthalocyanine as Photocatalyst.

In order to give an answer for the challenges of long wavelength-photocontrolled radical polymerization in aqueous solutions and to address the shortcomings of conventional near-infrared (NIR) photocatalysts (PCs) that are difficult to subject to post-treatment, we designed and synthesized a series of ß-tetra-substituted water-soluble zinc phthalocyanines (ß-TS-Zns) as the NIR PCs for reversible addition-fragmentation chain transfer (RAFT) polymerization successfully under irradiation with NIR (λmax = 730 nm) light at room temperature. Importantly, the NIR PCs can also be designed as polymerizable monomers and covalently loaded on the polymer chains, which are endowed with permanent NIR photocatalysis of the resultant polymers. Moreover, the polymerization can not only be carried out in water but also in phosphate buffer saline (PBS) solution, yielding polymers with controlled molar mass and narrow dispersities (D = 1.03-1.25). Therefore, this NIR-photocontrolled aqueous RAFT polymerization system may provide a charming strategy for possible applications in tissue engineering biomaterial in situ benefiting from the high penetration ability of NIR light.

Unimolecular micelles from star-shaped block polymers by photocontrolled BIT-RDRP for PTT/PDT synergistic therapy.

Unimolecular micelles (UIMs) exhibit promising potential in the precise diagnosis and accurate treatment of tumor tissues, a pressing problem in the field of medical treatment, because of their perfect stability in the complex and variable microenvironment. In this study, porphyrin-based four-armed star-shaped block polymers with narrow molar mass dispersity (D = 1.34) were facilely prepared by photocontrolled bromine-iodine transformation reversible-deactivation radical polymerization (BIT-RDRP). A photothermal conversion dye, ketocyanine, was covalently linked onto the PEG and then introduced into the polymers through a "grafting onto" strategy to obtain polymeric nanomaterial, THPP-4PMMA-b-4P(PEGMA-co-APMA)@NIR-800, with dual PTT/PDT function. The resulting polymers could form monodispersed UIMs in the water below critical aggregation concentration, meanwhile maintaining the capacities of singlet oxygen release and photothermal conversion. Importantly, the UIMs displayed excellent biocompatibility while exerting superior PTT and/or PDT therapeutic effects under the irradiation of specific wavelengths of light, according to in vitro cellular experiments, which is expected to become a new hot spot for cancer therapy and anti-tumor research. Overall, stable and powerful UIMs with dual PTT/PDT function is provided, which are expected to be competitive candidates in cancer therapy.