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

IF 5.3 2区化学 Q1 CHEMISTRY, ANALYTICAL

Microchimica Acta Pub Date : 2024-10-17 DOI:10.1007/s00604-024-06741-2

Sheng-Yan Yin, Yingcai Hu, Fengli Qu, Jin Li, Jishan Li

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Abstract

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.

Graphical Abstract

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四烷基炔基卟啉介导的金纳米团簇共价组装用于靶向肿瘤荧光成像和增强型光动力疗法

以纳米 Au8 簇为节点，5,10,15,20-四（4-烷基炔基苯基）卟吩（TEPP）为配体，开发了一种共价组装策略，以可控方式构建了基于金纳米簇的纳米组装（AuNCNA）。随后，通过点击反应对三肽精氨酸甘氨酸天冬氨酸（RGD）肽进行进一步修饰，从而构建了集靶向荧光成像和高效光动力疗法（PDT）于一体的多功能纳米平台（AuNCNA@RGD）。Au8 纳米簇和 TEPP 的强相互调节作用使 AuNCNA@RGD 表现出三个明显的优势：(i)TEPP在稳定Au8纳米团簇和保持活性位点固定在框架内发挥了重要作用，从而提高了Au8纳米团簇的稳定性；(ii)Au8纳米团簇具有可调能级，可加速光生电荷的转移，防止电子和空穴的重组，从而提高了TEPP用于PDT的光敏性；(iii)AuNCNA发出明亮的荧光，有助于RGD辅助的肿瘤靶向成像。该工作拓展了AuNC组装的构建方法，该组装方法具有多样性，可灵活转化不同的有机配体，构建各种基于AuNC的功能纳米材料。

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来源期刊

Microchimica Acta 化学-分析化学

CiteScore

9.80

自引率

5.30%

发文量

410

审稿时长

2.7 months

期刊介绍： As a peer-reviewed journal for analytical sciences and technologies on the micro- and nanoscale, Microchimica Acta has established itself as a premier forum for truly novel approaches in chemical and biochemical analysis. Coverage includes methods and devices that provide expedient solutions to the most contemporary demands in this area. Examples are point-of-care technologies, wearable (bio)sensors, in-vivo-monitoring, micro/nanomotors and materials based on synthetic biology as well as biomedical imaging and targeting.