Design and Synthesis of Metalloporphyrin Nanoconjugates for Dual Light-Responsive Antimicrobial Photodynamic Therapy.

Antimicrobial photodynamic therapy (APDT) utilizes photosensitizers (PSs) that eradicate a broad spectrum of bacteria in the presence of light and molecular oxygen. On the other hand, some light sources such as ultraviolet (UVB and UVC) have poor penetration and high cytotoxicity, leading to undesired PDT of the PSs. Herein, we have synthesized conjugatable mesosubstituted porphyrins and extensively characterized them. Time-dependent density functional theory (TD-DFT) calculations revealed that metalloporphyrin EP (5) is a suitable candidate for further applications. Subsequently, the metalloporphyrin was conjugated with lignin-based zinc oxide nanocomposites (ZnOAL and ZnOKL) to develop hydrophilic nanoconjugates (ZnOAL@EP and ZnOKL@EP). Upon dual light (UV + green light) exposure, nanoconjugates showed enhanced singlet oxygen generation ability and also demonstrated pH responsiveness. These nanoconjugates displayed significantly improved APDT efficiency (4-7 fold increase) to treat bacterial infection under dual light irradiation.

Synthesis of Metallo-Chromone Porphyrin Nano-Starch Sensitizers as Photodynamic Therapeutics for the Eradication of Enterococci Dental Pathogens.

Photodynamic therapy (PDT), as an advanced, alternative, and promising treatment, can inhibit dental pathogens. PDT employs the activation of photosensitizers via the light of a particular wavelength and molecular oxygen to inhibit dental pathogens. Herein, we present a comprehensive study on the synthesis and characterization of three chromone-porphyrins [Zn(II)-5-[4-chromone]-15-(4-phenyl)porphyrin (ZnCP), 5-[4-chromone]-15-(4-12 phenyl)porphyrin (DMCP), and Pd(II)-5-[4-chromone]-15-(4-phenyl)porphyrin (PdCP)]. Next, the computational study was also performed to establish the correlation between photophysical properties and theoretical calculations for those chromone-porphyrins using density functional theory and time-dependent density functional theory. Furthermore, chromone-porphyrins were encapsulated in starch nanoparticles to develop soluble nano-starch sensitizers (ZnCP-SNPs, DMCP-SNPs, and PdCP-SNPs) via the nanoprecipitation technique. Upon green light exposure, these nano-starch sensitizers exhibited excellent singlet oxygen generation ability. Moreover, final nanoformulations have been explored for pH responsiveness. Based on our intriguing findings, the chromone-porphyrin-loaded nano-starch sensitizers displayed great potential as prospective PDT to treat enterococci dental pathogens.