Wang Chen, Feng Luyao, Liu Junxiao, Fu Jing, Shen Jinglin, Qi Wei
School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, China.
Nanomaterials (Basel). 2022 Apr 25;12(9):1453. doi: 10.3390/nano12091453.
Au nanocluster (AuNCs)-based luminescent functional materials have attracted the interest of researchers owing to their small size, tractable surface modification, phosphorescence lifetime and biocompatibility. However, the poor luminescence quantum yield (QY) of AuNCs limits their practical applications. Herein, we synthesized a type of AuNCs modified by 4,6-diamino-2-mercaptopyrimidine hydrate (DPT-AuNCs). Furthermore, organic acids, i.e., citric acid (CA) and tartaric acid (TA), were chosen for co-assembly with DPT-AuNCs to produce AuNCs-based luminescent materials with enhanced emission. Firstly, it was found that CA could significantly enhance the emission of DPT-AuNCs with the formation of red emission nanofibers (QY = 17.31%), which showed a potential for usage in I detection. The ···π/π···π interaction between the CA and the DPT ligand was proposed as crucial for the emission. Moreover, chiral TA could not only improve the emission of DPT-AuNCs, but could also transfer its chirality to DPT-AuNCs and induce the formation of circularly polarized luminescence (CPL)-active nanofibers. It was demonstrated that the CPL signal could increase 4.6-fold in a ternary CA/TA/DPT-AuNCs co-assembly system. This work provides a convenient way to build AuNCs-based luminescent materials as probes, and opens a new avenue for building CPL-active materials by achiral NCs through a co-assembly strategy.
基于金纳米团簇(AuNCs)的发光功能材料因其尺寸小、易于进行表面修饰、具有磷光寿命和生物相容性而吸引了研究人员的关注。然而,AuNCs较差的发光量子产率(QY)限制了它们的实际应用。在此,我们合成了一种由4,6-二氨基-2-巯基嘧啶水合物修饰的AuNCs(DPT-AuNCs)。此外,选择有机酸,即柠檬酸(CA)和酒石酸(TA),与DPT-AuNCs进行共组装,以制备具有增强发射的基于AuNCs的发光材料。首先,发现CA能通过形成红色发射纳米纤维(QY = 17.31%)显著增强DPT-AuNCs的发射,这显示出其在碘检测中的应用潜力。CA与DPT配体之间的···π/π···π相互作用被认为对发射至关重要。此外,手性TA不仅能改善DPT-AuNCs的发射,还能将其手性传递给DPT-AuNCs并诱导形成圆偏振发光(CPL)活性纳米纤维。结果表明,在三元CA/TA/DPT-AuNCs共组装体系中,CPL信号可增加4.6倍。这项工作提供了一种构建基于AuNCs的发光材料作为探针的简便方法,并通过共组装策略为利用非手性纳米团簇构建CPL活性材料开辟了一条新途径。