Citation: GUO Xiaohong, ZHOU Ying, SHI Lihong, ZHANG Yan, ZHANG Caihong, DONG Chuan, ZHANG Guomei, SHUANG Shaomin. Luminescence Emission of Copper Nanoclusters by Ethanol-induced Aggregation and Aluminum Ion-induced Aggregation[J]. Acta Physico-Chimica Sinica, ;2018, 34(7): 818-824. doi: 10.3866/PKU.WHXB201712081 shu

Luminescence Emission of Copper Nanoclusters by Ethanol-induced Aggregation and Aluminum Ion-induced Aggregation

School of Chemistry and Chemical Engineering, Institute of Environmental Science, Shanxi University, Taiyuan 030006, P. R. China

Corresponding author: ZHANG Guomei, gmzhang@sxu.edu.cn SHUANG Shaomin, smshuang@sxu.edu.cn
Received Date: 3 November 2017
Revised Date: 4 December 2017
Accepted Date: 4 December 2017
Available Online: 8 July 2017
Fund Project: Primary Research and Development Plan of Shanxi Province, China 201703D321031The project was supported by the National Natural Science Foundation of China (21475080, 21571116, 21575084), Program for the Top Young and Middle-aged Innovative Talents of Higher Learning Institutions of Shanxi Province, China (TYMIT), Shanxi Province Hundred Talent Project, the Youth Science Foundation of Shanxi Province, China (201701D221029) and Primary Research and Development Plan of Shanxi Province, China (201703D321031)Program for the Top Young and Middle-aged Innovative Talents of Higher Learning Institutions of Shanxi Province, China TYMITthe National Natural Science Foundation of China 21575084the Youth Science Foundation of Shanxi Province, China 201701D221029the National Natural Science Foundation of China 21571116the National Natural Science Foundation of China 21475080

Metal nanoclusters (MNCs), as a new type of nano-material, possess excellent properties such as facile synthesis, strong light stability, low toxicity, excellent biocompatibility, and high luminous efficiency. Aggregation-induced emission (AIE), which can enhance the luminescence properties of MNCs, has resulted in MNCs attracting significant attention. In this thesis, L-glutathione (GSH)-protected copper nanoclusters (GS@CuNCs) were prepared by a "one-pot" method in aqueous solution without additional reducing agents. The GS@CuNCs were characterized by UV-Vis absorption spectroscopy and fluorescence spectroscopy. Upon excitation at 370 nm, the fluorescence spectrum of GS@CuNCs displayed the maximum emission peak at 610 nm. The as-prepared CuNCs generate a striking fluorescence intensity via aggregation-induced emission (AIE). The AIE property of GS@CuNCs was examined for the aggregates in different organic solvents, such as ethanol, methanol, and dimethylformamide. Since the aggregation degree was controlled by the content of organic solvent, we further measured the fluorescence intensity of GS@CuNCs in different volume ratios of a water-ethanol mixture solution. The fluorescence intensity of GS@CuNCs exhibited an approximately 30-fold increase at 85% of ethanol content, as compared to that in aqueous solution. A possible mechanism may be that intramolecular motions are restricted in ethanol, resulting in a significant increase of fluorescence intensity. Moreover, only very weak emissions were recorded for the CuNC dispersion in aqueous solution; however, an apparent luminescence enhancement was observed in both luminescence spectra and by naked eyes under UV light, with a gradual increase in the ethanol content in the water-ethanol mixture from 0% to 85%. Additionally, we developed a new selective and sensitive turn-on fluorescent sensor for the detection of trivalent aluminum ions (Al³⁺) based on cation-induced aggregation methods. Among the 15 types of metal cations studied, only Al³⁺ visibly increased the fluorescence emission of the GS@CuNCs. These results indicated that the GS@CuNCs were highly selective to Al³⁺ than other metal ions, which may result from the electrostatic and coordination interactions between the trivalent aluminum ions and monovalent carboxylic anions from GSH in the CuNCs. The response of the probe to Al³⁺ exhibited a good linear range of 2–20 μmol·L^-1 and the detection limit was 33 nmol·L^-1. Thus, the weak fluorescence intensity of CuNCs was increased markedly by the AIE of Al³⁺, and could construct an interesting fluorescent platform for sensing aluminum ions. The property of AIE of GS@CuNCs may expand the potential applications of nanocluster materials to biosensors and cell imaging.
- Fluorescence,
- Copper nanoclusters,
- Aggregation-induced emission,
- Ethanol,
- Aluminum ion
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