Self‐assembly of Amphiphilic Porphyrins To Construct Nanoparticles for Highly Efficient Photodynamic Therapy

Abstract

Hydrophobic photosensitizers greatly affect cell permeability and enrichment in tumors, but they cannot be used directly for clinical applications because they always aggregate in water, preventing their circulation in the blood and accumulation in tumor cells. As a result, amphiphilic photosensitizers are highly desirable. Although nanomaterialbased photosensitizers can solve water solubility, they have the disadvantages of complicated operation, poor reproducibility, low drug loading, and poor stability. In this work, an efficient synthesis strategy is proposed that converts small molecules into nanoparticles in 100 % aqueous solution by molecular assembly without the addition of any foreign species. Three photosensitizers with triphenylphosphine units and ethylene glycol chains of different lengths, TPPÀ PPh 3 , TPPÀ PPh 3 À 2PEG and TPPÀ PPh 3 À 4PEG, were synthesized to improve amphiphilicity. Of the three photosensitizers, TPPÀ PPh 3 À 4PEG is the most efficient (singlet oxygen yield: 0.89) for tumor photodynamic therapy not only because of its definite constituent, but also because its amphiphilic structure allows it to self-assemble in water.

Porphyrin‐Based Nanoparticles: A Promising Phototherapy Platform

“…Compared with the amphiphilic porphyrin nanoparticles synthesized by Wang et al. in 2018, the amphiphilic porphyrin nanoparticles synthesized by Jiang et al [45] . not only had better water solubility, but also had higher antitumor activity and tumor targeting.…”

“…TPP‐GA NPs [44] , TPP‐PPh 3 ‐4PEG NPs [45] , PEG‐Por‐CD: oxli Pt(IV)‐ada [105] , DOX@TPP‐PEG‐biotin SANs [109] , cRGDAu PNSs [119] , Por NPs and ZnPor NPs [126] , NI‐Por NPs and NI‐ZnPor NPs [127] , PGL‐DiR NPs [181] , POL‐DPP NPs [196] , PGL‐DOX NPs [182] …”

Multiporphyrinic architectures: Advances in structural design for photodynamic therapy

“…Por [4]; Por [6]; Por [8] Direct coupling EET rates: (119 fs) −1 , (342 fs) −1 , (236 fs) −1 [28] Por [12]; Por [24] m-Phenylene linking EET rates: (3.6 ps) −1 , (35 ps) −1 [29][30] Por [12] COF-366 TAPP, 1 Photoacoustic-guided PDT and PTT for cancer therapy [46] PFCE@THPP pf -PEG THPP, PFSEA, PFCE Oxygen nanoshuttles for enhanced PDT and tumor hypoxia relief [47] COF@GOx&CAT TAPP, 2, GOx/CAT Long-term starvation and enhanced PDT of cancer [48] TP-Por CON@BNN6 DBPP, HHTP, BNN6 PDT, PTT and GT therapy of chronic wound infection [49] Others TPP-PPh 3 -4PEG NPs TPP-PPh 3 -4PEG Amphiphilic NPs for highly efficient PDT [50] GOx/CAT-NCs TPPP-tyr, GOx/CAT Porphyrin capsule for starvation and PDT of cancer [51] Abbreviations: MOFs, metal-organic frameworks; COFs, covalent-organic frameworks; PDT, photodynamic therapy; PTT, photothermal therapy.…”

“…Apart from the multiporphyrin nanoarrays and porphyrinic frameworks, some others porphyrinic assemblies, including but not limited to amphiphilic micelles, [50] vesicles, [123] monolayered capsules, [124] have been widely used for high efficient PDT therapy. For example, Bai and Fan et al report a porphyrin nanoparticle through porphyrin assembly, which can be further surrounded by amorphous silica layer through silicate sol-gel process to make core-shell porphyrinic structures.…”

“…The nanoparticles also show high 1 O 2 yields for photodynamic therapy (Figure 10A). [50] Besides, Shi and co-workers reported a self-assembly strategy for producing biomimetic (Gd/Zn) porphyrin nanostructures with enhanced photodynamic therapy. [127] Lai reported a robust and uniform porphysome through amphiphilic self-assembly strategy, which indicated to be an efficient PDT agents for theranostic applications.…”