Yan Bingjie, Duan Mulin, Chen Bijia, Zheng Haoran, Zhou Yan, Zhou Gaoang, Zhang Siyuan, Wang Jiabin, Yao Guangbao, Zhu Ying, Li Jiang, Jia Sisi, Fan Chunhai, Chen Jing, Shen Jianlei
State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules and National Center for Translational Medicine, Shanghai Jiao Tong University, Shanghai 200240, China.
Jiaxing Key Laboratory of Biosemiconductors, Xiangfu Laboratory, Jiashan, Zhejiang 314102, China.
ACS Appl Mater Interfaces. 2025 Jul 23;17(29):42443-42453. doi: 10.1021/acsami.5c09616. Epub 2025 Jul 12.
The photoluminescent properties of atomically precise metal nanoclusters (MCs) have attracted intense interest in bioimaging and optical device applications, which are restricted by the limited brightness of MCs. In this study, we developed a single stranded (ss-) DNA-based ligand engineering approach to engineer highly luminescent and chiral MCs by transferring weakly luminescent clusters from the organic phase to the aqueous phase. Significantly, the luminescence quantum yield of the MCs was increased by up to 2 orders of magnitude (∼89-fold, reaching ∼56.18%), and the photoluminescence intensity was enhanced by up to 3 orders of magnitude (∼2127-fold) as compared to those in the organic phase. Using a set of theoretical and experimental studies including molecular dynamics simulations and ultrafast transient absorption spectroscopy, we established that the hydrophobic confinement of ssDNA on the cluster surface suppressed nonradiative transitions of excited-state clusters and reduced ligand motion at the cluster interface, which led to a fluorescence-to-phosphorescence transition that greatly contributed to the luminescence enhancement. We further observed that the chiral nature of ssDNA endowed chirality selection with a highly selective fluorescence enhancement for chiral MCs. This ssDNA-based ligand engineering approach provides a universal and powerful means for the development of water-dispersed, high-brightness photoluminescent materials for advanced optical applications.
原子精确的金属纳米团簇（MCs）的光致发光特性在生物成像和光学器件应用中引起了强烈关注，但其受到MCs有限亮度的限制。在本研究中，我们开发了一种基于单链（ss-）DNA的配体工程方法，通过将弱发光团簇从有机相转移到水相来设计高发光且具有手性的MCs。值得注意的是，与有机相中的MCs相比，MCs的发光量子产率提高了多达2个数量级（约89倍，达到约56.18%），光致发光强度增强了多达3个数量级（约2127倍）。通过一系列理论和实验研究，包括分子动力学模拟和超快瞬态吸收光谱，我们确定了ssDNA在团簇表面的疏水限制抑制了激发态团簇的非辐射跃迁，并减少了团簇界面处配体的运动，这导致了荧光到磷光的转变，极大地促进了发光增强。我们进一步观察到，ssDNA的手性赋予了手性选择，对手性MCs具有高度选择性的荧光增强。这种基于ssDNA的配体工程方法为开发用于先进光学应用的水分散、高亮度光致发光材料提供了一种通用且强大的手段。
