TY - JOUR
T1 - Value of the Debris of Reduction Sculpture
T2 - Thiol Etching of Au Nanoclusters for Preparing Water-Soluble and Aggregation-Induced Emission-Active Au(I) Complexes as Phosphorescent Copper Ion Sensor
AU - Shu, Tong
AU - Su, Lei
AU - Wang, Jianxing
AU - Lu, Xin
AU - Liang, Feng
AU - Li, Chenzhong
AU - Zhang, Xueji
N1 - Funding Information:
We are grateful for the financial support from the National Natural Science Foundation of China (Grant Nos. 21175010, 21545012, and 21275017), the Project-sponsored by SRF for ROCS, SEM, and the Fundamental Research Funds for the Central Universities (FRF-TP-15-096A1).
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/6/7
Y1 - 2016/6/7
N2 - Chemical etching of gold by thiols has been known to be capable of generating nonluminescent gold(I) complexes, e.g., in size-focusing synthesis of atomically precise gold nanoclusters (GNCs). These nonluminescent gold(I) complexes have usually been considered as useless or worthless byproducts. This study shows a promising potential of thiol etching of GNCs to prepare novel water-soluble and phosphorescent gold(I) materials for sensing application. First, cysteamine-induced etching of GNCs is used to produce nonluminescent oligomeric gold(I)-thiolate complexes. Then, cadmium ion induces the aggregation of these oligomeric complexes to produce highly water-soluble ultrasmall intra-aggregates. These intra-aggregates can phosphoresce both in dilute aqueous solutions and in the solid phase. Studies on the effect of pH on their phosphorescent emission reveal the importance of the interaction between the amino groups of the ligands and cadmium ion for their phosphorescent emission property. Furthermore, Cu2+ ion is found to quickly quench the phosphorescent emission of the intra-aggregates and simultaneously cause a Cu2+-concentration-dependent peak wavelength shift, enabling the establishment of a novel colorimetric sensor for sensitive and selective visual sensing of Cu2+.
AB - Chemical etching of gold by thiols has been known to be capable of generating nonluminescent gold(I) complexes, e.g., in size-focusing synthesis of atomically precise gold nanoclusters (GNCs). These nonluminescent gold(I) complexes have usually been considered as useless or worthless byproducts. This study shows a promising potential of thiol etching of GNCs to prepare novel water-soluble and phosphorescent gold(I) materials for sensing application. First, cysteamine-induced etching of GNCs is used to produce nonluminescent oligomeric gold(I)-thiolate complexes. Then, cadmium ion induces the aggregation of these oligomeric complexes to produce highly water-soluble ultrasmall intra-aggregates. These intra-aggregates can phosphoresce both in dilute aqueous solutions and in the solid phase. Studies on the effect of pH on their phosphorescent emission reveal the importance of the interaction between the amino groups of the ligands and cadmium ion for their phosphorescent emission property. Furthermore, Cu2+ ion is found to quickly quench the phosphorescent emission of the intra-aggregates and simultaneously cause a Cu2+-concentration-dependent peak wavelength shift, enabling the establishment of a novel colorimetric sensor for sensitive and selective visual sensing of Cu2+.
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U2 - 10.1021/acs.analchem.6b01450
DO - 10.1021/acs.analchem.6b01450
M3 - Article
AN - SCOPUS:84974578137
VL - 88
SP - 6071
EP - 6077
JO - Analytical Chemistry
JF - Analytical Chemistry
SN - 0003-2700
IS - 11
ER -