Deng Hao-Hua, Huang Kai-Yuan, Zhu Chen-Ting, Shen Jian-Feng, Zhang Xiang-Ping, Peng Hua-Ping, Xia Xing-Hua, Chen Wei
Higher Educational Key Laboratory for Nano Biomedical Technology of Fujian Province, Department of Pharmaceutical Analysis, Fujian Medical University, Fuzhou 350004, China.
State Key Laboratory of Analytical Chemistry for Life Science and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
J Phys Chem Lett. 2021 Jan 21;12(2):876-883. doi: 10.1021/acs.jpclett.0c03617. Epub 2021 Jan 11.
Although metal nanoclusters (MNCs) have shown great promise for the further development of photochemical techniques to be applied in diverse areas (e.g., photoelectronic devices, photochemical sensors, photocatalysts, and energy storage and conversion systems), the fundamental problem of their electron transfer behavior still remains unsolved. Herein, a driving force-dependent photoinduced electron transfer process of gold nanoclusters (AuNCs) is clarified for the first time from a rational-designed opposite-charged system. It was found that the electron transfer dynamic of carboxylated chitosan and dithiothreitol-commodified AuNCs (CC/DTT-AuNCs) can be satisfactorily described by the Marcus electron transfer theory. This proved model was applied to estimate the ultrafast charge separation process between CC/DTT-AuNCs and mitoxantrone, which was confirmed by fluorescence quenching and femtosecond transient absorption spectroscopy measurements. We envision that this work will open a new door for understanding the electron transfer behavior of MNCs and facilitate the design of advanced optoelectronic devices.
尽管金属纳米团簇（MNCs）在光化学技术的进一步发展中展现出巨大潜力，有望应用于多个领域（如光电器件、光化学传感器、光催化剂以及能量存储与转换系统），但其电子转移行为的基本问题仍未得到解决。在此，首次从一个合理设计的带相反电荷的体系中阐明了金纳米团簇（AuNCs）的驱动力依赖型光致电子转移过程。研究发现，羧甲基壳聚糖和二硫苏糖醇修饰的金纳米团簇（CC/DTT-AuNCs）的电子转移动力学可以用Marcus电子转移理论得到令人满意的描述。该经过验证的模型被用于估算CC/DTT-AuNCs与米托蒽醌之间的超快电荷分离过程，这一过程通过荧光猝灭和飞秒瞬态吸收光谱测量得到了证实。我们设想这项工作将为理解MNCs的电子转移行为打开一扇新的大门，并促进先进光电器件的设计。
