Distance, orientation, and number controlled porphyrin-peptoid conjugates (PPCs) were efficiently synthesized. Cofacial (1, 2, and 4), slipped-cofacial (3), and unstructured (5) arrangements of porphyrins provided distinct optical and electronic properties characterized by UV-vis and circular dichroism spectroscopy. In addition, ECCD spectra confirmed the handedness of peptoid helices.
Photopolymerization of hydrogels has been widely used to encapsulate cells and support their growth in 3D environments. However, common light sources (i.e., ultraviolet and visible light) strongly interact with biological systems and are therefore inappropriate for in vivo applications, such as transdermal polymerization. Using near infrared (NIR) light that minimally interacts with living tissues, this study investigates NIR light-assisted photothermal polymerization (NAPP) of diacrylated polyethylene glycol (PEGDA), in which interactions between NIR light and gold nanorods activate a thermal initiator (i.e., AIPH), resulting in generation of radicals for polymerization of PEGDA. Gelation parameters, including precursor concentrations and NIR power, are investigated to minimize the use of initiator and temperature increases (<43 °C) during NAPP. Cell viability is as high as 80% after NAPP-based encapsulation. Incorporation of polyethylene glycol (PEG) modified with a cell-adhesive peptide moiety (Arg-Gly-Asp) into the gel system further enables prolongation of cell viability during incubation up to 7 d. NAPP results in successful transdermal gelation and good viability of the transplanted cells. Thus, this new cell encapsulation approach, demonstrated for the first time in this study, will benefit various applications, including cell delivery and remote control over cellular environments.
Light-induced polymerization has been widely applied for hydrogel synthesis, which conventionally involves the use of ultraviolet or visible light to activate a photoinitiator for polymerization. However, with these light sources, transdermal gelation is not efficient and feasible due to their substantial interactions with biological systems, and thus a high power is required. In this study, we used biocompatible and tissue-penetrating near infrared (NIR) light to remotely trigger a thiol-acrylate reaction for efficient in vivo gelation with good controllability. Our gelation system includes gold nanorods as a photothermal agent, a thermal initiator, diacrylate polyethylene glycol (PEG), and thiolated PEG. Irradiation with a low-power NIR laser (0.3 W cm(-2)) could induce gelation via a mixed-mode reaction with a small increase in temperature (∼5 °C) under the optimized conditions. We also achieved successful transdermal gelation via the NIR-assisted photothermal thiol-acryl reactions. This new type of NIR-assisted thiol-acrylate polymerization provides new opportunities for in situ hydrogel formation for injectable hydrogels and delivery of drugs/cells for various biomedical applications.
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