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ACS Appl Mater Interfaces. 2018 Nov 21;10(46):40132-40140. doi: 10.1021/acsami.8b13594. Epub 2018 Nov 12.

Cyclomatrix Polyphosphazene Porous Networks with J-Aggregated Multiphthalocyanine Arrays for Dual-Modality Near-Infrared Photosensitizers.

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State Key Laboratory of Molecular Engineering of Polymers, and Department of Macromolecular Science , Fudan University , Shanghai 200433 , P. R. China.
National Nanotechnology Center (NANOTEC) , National Science and Technology Development Agency , Pathumthani 12120 , Thailand.
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience , National Center for Nanoscience and Technology , Beijing 100190 , P. R. China.


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 D3 h 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.


conjugated porous polymers; metallophthalocyanine; near-infrared light; photothermal/photodynamic therapy; polyphosphazene


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