Design and Synthesis of Nanoscale Zr-Porphyrin Ⅸ Framework for Syner-gistic Photodynamic and Sonodynamic Therapy of Tumors
Multifunctional nanomaterials with photodynamic and sonodynamic properties have attracted wide attention in tumor therapy,but the design and preparation of"all-in-one"type of multifunctional nanomaterials with single component remains challenging.Herein the"all-in-one"type of Zr-PpⅨ(protoporphyrin Ⅸ)coordination nanoparticles(ZrPs)with photodynamic and sonodynamic properties was reported as efficient nano-photo/sonosensitizers.The ZrPs had an average size of about 50 nm.The survey X-ray photoelectron spectroscopy(XPS)spectrum showed strong Zr,C,N and O elemental signals,verifying that the ZrPs were composed of Zr/C/N/O elements.In addition,Fourier transform infrared(FTIR)spectra,ultraviolet-visible(UV-Vis)spectra and fluorescence(FL)spectra showed that the Zr4+ion was only coordinated with the carboxyl group of PpⅨ.The ZrPs contained photo/sono-sensitizers PpⅨ,which could be excited by light/ultrasonic(US)to transform O2 into cytotoxic 1O2.Furthermore,the 1O2 can be detected by using 1,3-diphenylisobenzofuran(DPBF)assay.When the mixed solution(ZrPs+DPBF)was excited by light,the peak of DPBF decreased rapidly as the light irradiation time increased,which suggested the generation of 1O2 by ZrPs+light.Similarly,the absorbance of DPBF+ZrPs was reduced as the US time increased,which confirmed the sonodynamic effect of ZrPs+US.After 5 min of light/US irradiation,59.7％(light)and 22.8％(US)of DPBF was found to be oxidized by ZrPs,which showed effective ROS generation for photody-namic/sonodynamic therapy.Besides,ZrPs had shown good biosafety in vitro cellular experiments.ZrPs can be effectively endocytosed/uptaken by tumor cells.Meanwhile,ZrPs within cells can generate ROS upon light/US,affording photodynamic and/or sonodynamic effects.After 5 min of ZrPs with light/US irradiation,the cell viability goes down rapidly from about 100％to 5.3％.Therefore,the present study not only represents ZrPs as an"all-in-one"type of multifunctional nanomaterials for PDT-SDT therapy,but also provides some insights for designing other PpⅨ-related molecules with the similar structure for bioapplication.
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