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Here, we have developed a kind of cyclomatrix polyphosphazene with excellent photophysical properties and pursued their potential of being organic photosensitizers for dual-modality phototherapy. Briefly, hexachlorocyclophosphazene (HCCP) with D symmetry is adopted as a synthon to attach Zn(II) phthalocyanine (ZnPc) to form dendritic units that are covalently expanded into a soluble porous network through the nucleophilic substitution reaction. Molecular simulation reveals that the multi-ZnPc units around HCCP can be oriented in a side-by-side manner, leading to the remarkably red-shifted and intense absorbance in the near-infrared (NIR) region. To validate the potential in bioapplication, such ZnPc-based polyphosphazenes are assembled by incorporation of polyvinylpyrrolidone (PVP) to produce the uniform nanoparticles with aqueous dispersibility and biocompatibility. From the in vitro results, the PVP-stabilized photosensitizing nanoparticles can undergo the photothermal/photodynamic processes to concurrently generate heat and singlet oxygen for efficiently killing cancer cells upon exposure to a single-bandwidth NIR laser (785 nm). Compared with the known organic photosensitizers, cyclomatrix polyphosphazene would be a promising platform to configure a diversity of reticular arrays with dense and oriented arrangement of dye molecules, leading to their largely enhanced photophysical and photochemical properties.
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http://dx.doi.org/10.1021/acsami.8b13594 | DOI Listing |
J Colloid Interface Sci
August 2024
National Engineering Research Center of Flame Retardant Materials, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, PR China.
Cyclomatrix polyphosphazenes have attracted widespread attention in the field of polymer flame retardancy. Nevertheless, the optimal manifestation of their distinctive structural attributes and flame-retardant properties necessitates a judicious selection of condensation monomers and synergistic templates during the fabrication of polyphosphazene flame retardants. In our previous studies, it was discovered that when ZIF-67 is functionalized with polyphosphazene, the by-product HCl from phosphazene polycondensation causes etching on ZIF-67.
View Article and Find Full Text PDFACS Omega
March 2023
Department of Chemistry, University of Quebec at Montreal, Montreal, Quebec H3C 3P8, Canada.
Highly cross-linked inorganic and organic hybrid cyclomatrix-polyphosphazenes microspheres (C-PPZs) have been successfully synthesized by a one-pot polymerization technique between hexachlorocyclotriphosphazene and -phenylenediamine in the presence of triethylamine (TEA), and they were used for enhancing the flame retardancy of epoxy resins (EPs). A thermoset EP was prepared by incorporating different percentages (2, 5, and 10%) of C-PPZs into diglycidyl ether of bisphenol A (DGEBA). The results reveal that the size and morphology of the microspheres can be tuned by varying the synthesis temperature.
View Article and Find Full Text PDFACS Appl Polym Mater
March 2023
Membrane Science and Technology Cluster, Faculty of Science and Technology, MESA Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands.
A series of cyclomatrix polyphosphazene films have been prepared by nonaqueous interfacial polymerization (IP) of small aromatic hydroxyl compounds in a potassium hydroxide dimethylsulfoxide solution and hexachlorocyclotriphosphazene in cyclohexane on top of ceramic supports. Via the amount of dissolved potassium hydroxide, the extent of deprotonation of the aromatic hydroxyl compounds can be changed, in turn affecting the molecular structure and permselective properties of the thin polymer networks ranging from hydrogen/oxygen barriers to membranes with persisting hydrogen permselectivities at high temperatures. Barrier films are obtained with a high potassium hydroxide concentration, revealing permeabilities as low as 9.
View Article and Find Full Text PDFMolecules
December 2022
Department of Chemistry, School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology, Northwestern Polytechnical University, Xi'an 710129, China.
The [VO] cluster is successfully immobilized to the polymeric framework of cyclomatrix polyphosphazene via the facile precipitation polymerization between the phenol group symmetrically modified [VO] and hexachlorocyclotriphosphazene. The structure of the as-prepared polyoxometalate-containing polyphosphazene (HCCP-V) was characterized by FT-IR, XPS, TGA, BET, as well as SEM and zeta potential. The presence of a rigid polyoxometalate cluster not only supports the porous structure of the polymeric framework but also provides an improved catalytic oxidation property.
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August 2022
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, P. R. China.
Polyphosphazenes are an inorganic molecular hybrid family with multifunctional properties due to their wide range of organic substitutes. This review intends to propose the basics of the synthetic chemistry of polyphosphazene, describing for researchers outside the field the basic knowledge required to design and prepare polyphosphazenes with desired properties. A special emphasis is placed on recent advances in chemical synthesis, which allow not only the synthesis of polyphosphazenes with controlled molecular weights and polydispersities but also the synthesis of novel branched designs and block copolymers.
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