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Ultrastable atomically precise chiral silver clusters with more than 95% quantum efficiency.

ABSTRACT: Monolayer-protected atomically precise silver clusters display low photoluminescence (PL) quantum yield (QY) and susceptibility under ambient conditions, and their chiroptical activities also remain underdeveloped. Here, we report enantiomers of an octahedral Ag6 cluster prepared via one-step synthesis using designed chiral ligands at ambient temperature. These clusters exhibit a highest PLQY (300 K) >95.0% and retain their structural integrity and emission up to 150°C in air. Atomically precise structural determination combined with photophysical and computational analysis revealed that thermally activated delayed fluorescence, observed in silver cluster systems, is responsible for the high PLQY, which combines chirality in excited states to generate strong circularly polarized luminescence. These unprecedented findings open up horizons of investigation of monolayer-protected silver clusters for future luminescence applications.

SUBMITTER: Han Z

PROVIDER: S-EPMC7007243 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Ultrastable atomically precise chiral silver clusters with more than 95% quantum efficiency.

Han Zhen Z Dong Xi-Yan XY Luo Peng P Li Si S Wang Zhao-Yang ZY Zang Shuang-Quan SQ Mak Thomas C W TCW

Science advances 20200207 6

Monolayer-protected atomically precise silver clusters display low photoluminescence (PL) quantum yield (QY) and susceptibility under ambient conditions, and their chiroptical activities also remain underdeveloped. Here, we report enantiomers of an octahedral Ag<sub>6</sub> cluster prepared via one-step synthesis using designed chiral ligands at ambient temperature. These clusters exhibit a highest PLQY (300 K) >95.0% and retain their structural integrity and emission up to 150°C in air. Atomica ...[more]

PMID: 32083176

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Project description:BackgroundAs we know, radiotherapy plays an irreplaceable role in the clinical management on solid tumors. However, due to the non-specific killing effects of ionizing radiation, normal tissues damages would be almost simultaneous inevitably. Therefore, ideal radioprotective agents with high efficiency and low toxicity are always desirable. In this work, atomically precise Ag14 clusterzymes were developed, and their applications in radioprotection were studied in vitro and in vivo for the first time.MethodsThe ultra-small glutathione supported Ag14 clusterzymes were synthesized by convenient sodium borohydride (NaBH4) reduction of thiolate-Ag (I) complexes and then they were purified by desalting columns. The enzyme-like activity and antioxidant capacity of Ag14 clusterzymes have been tested by various commercial kits, salicylic acid method and electron spin resonance (ESR). Next, they were incubated with L929 cells to evaluate whether they could increase cell viability after γ-ray irradiation. And then Ag14 clusterzymes were intravenously injected into C57 mice before 7 Gy whole-body γ-ray irradiation to evaluate the radioprotection effects in vivo. At last, the in vivo toxicities of Ag14 clusterzymes were evaluated through biodistribution test, hematological details, serum biochemical indexes and histological test in female Balb/c mice with intravenous injection of Ag14 clusterzymes.ResultsOur studies suggested atomically precise Ag14 clusterzymes were potential radioprotectants. Ag14 clusterzymes exhibited unique superoxide dismutase (SOD)-like activity, strong anti-oxidative abilities, especially on •OH scavenging. The Ag14 clusterzymes could effectively improve cell viability through eliminating ROS and prevent DNA damages in cells dealt with γ-ray irradiation. In vivo experiments showed that Ag14 clusterzymes could improve the irradiated mice survival rate by protecting hematological systems and repairing tissue oxidative stress damage generated by γ-ray irradiation. In addition, bio-distribution and toxicological experiments demonstrated that the ultrasmall Ag14 clusterzymes could be excreted quickly from the body by renal clearance and negligible toxicological responses were observed in mice up to 30 days.ConclusionIn summary, atomically precise, ultrasmall and water soluble Ag14 clusterzymes with SOD-like activity were successfully developed and proved to be effective both in vitro and in vivo for radioprotection. Furthermore, with atomically precise molecular structure, Ag14 clusterzymes, on aspect of the catalytic and optical properties, may be improved by structure optimization on atom-scale level for other applications in disease diagnosis and treatment.

Dataset Information

Ultrastable atomically precise chiral silver clusters with more than 95% quantum efficiency.

Publications

Ultrastable atomically precise chiral silver clusters with more than 95% quantum efficiency.

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