Tetraalkynylporphyrin-mediated covalent assembly of gold nanoclusters for targeted tumor fluorescence imaging and enhanced photodynamic therapy

A covalent assembly strategy was developed to construct a gold nanocluster-based nano-assembly (AuNCNA) in a controllable manner, using Au₈ nanocluster as node and 5,10,15,20-tetra(4-alkynylphenyl)porphine (TEPP) as ligand. Subsequently, the tripeptide arginine glycine aspartic acid (RGD) peptide is further modified via clicking reaction to build a multi-functional nanoplatform (AuNCNA@RGD) that can integrate the targeted fluorescence imaging and efficient photodynamic therapy (PDT). The strong interregulation of Au₈ nanocluster and TEPP results in AuNCNA@RGD exhibiting three distinct advantages: (i) TEPP plays an important role in stabilizing the Au₈ nanocluster and keeping the active site fixed within the framework, thereby enhancing stability of Au₈ nanocluster; (ii) Au₈ nanocluster possess adjustable energy level, which can accelerate the transfer of photogenerated charge and prevent the recombination of electrons and holes, thus improving the photosensitivity of TEPP for PDT; (iii) AuNCNA exhibits bright fluorescence emission that facilitates RGD-assisted targeted tumor imaging. This work expands the construction method of AuNC assembly, and this assembly method is versatile and can flexibly transform different organic ligands to construct various AuNC-based functional nanomaterials.