Su Yu, Yuan Baozhen, Jiang Yaowen, Wu Ping, Huang Xiaolin, Zhu Jun-Jie, Jiang Li-Ping
State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University Nanjing Jiangsu 210023 China.
State Key Laboratory of Food Science and Technology, School of Food Science and Technology, Nanchang University Nanchang 330047 China.
Chem Sci. 2022 May 12;13(22):6573-6582. doi: 10.1039/d2sc01534j. eCollection 2022 Jun 7.
Surface-enhanced Raman scattering (SERS) based on chemical mechanism (CM) has great potential for superior stability and selectivity. Moreover, a bioinspired CM-Raman substrate-Raman reporter system with charge separation and electron transport nature provides thylakoid-mimicking potential for multifunctional applications. Herein, hollow carbon nitride nanospheres hierarchically assembled with a well-oriented copper(ii) phthalocyanine layer and hyaluronic acid (HCNs@CuPc@HA) were designed as a light-harvesting nanocomposite and photosynthesis-mimicking nanoscaffold that enhance both CM-SERS and photoredox catalysis. Remarkable SERS enhancement was achieved due to the strengthened short-range substrate-molecule interaction, enriched CuPc molecule loading and enhanced light-mater interactions. Meanwhile, the uniform CuPc molecule film mimics a photo-pigment to accelerate the near infrared (NIR)-oxygen generation and photodynamic catalysis of photosynthetic membrane-like HCNs. The experimental findings were further validated by numerical theory analysis. The greatly enhanced SERS signal and photosynthetic-mimicking properties of the heterostructure (denoted as HCNCHs) were successfully employed for circulating tumor cell (CTC) diagnosis and SERS imaging-guided cancer catalytic therapy in tumor xenograft models.
基于化学机制（CM）的表面增强拉曼散射（SERS）在稳定性和选择性方面具有巨大潜力。此外，具有电荷分离和电子传输特性的仿生CM-拉曼底物-拉曼报告系统为多功能应用提供了类囊体模拟潜力。在此，设计了由取向良好的铜（II）酞菁层和透明质酸分层组装的中空氮化碳纳米球（HCNs@CuPc@HA）作为光捕获纳米复合材料和模拟光合作用的纳米支架，以增强CM-SERS和光氧化还原催化。由于增强的短程底物-分子相互作用、丰富的铜酞菁分子负载和增强的光-物质相互作用，实现了显著的SERS增强。同时，均匀的铜酞菁分子膜模拟光色素，以加速类光合膜HCNs的近红外（NIR）氧生成和光动力催化。通过数值理论分析进一步验证了实验结果。异质结构（表示为HCNCHs）大大增强的SERS信号和模拟光合作用特性成功用于肿瘤异种移植模型中的循环肿瘤细胞（CTC）诊断和SERS成像引导的癌症催化治疗。
