Research paperFluorescent determination of fluazinam with polyethyleneimine-capped copper nanoclusters
Graphical abstract
A PEI-functionalized Cu NCs was employed to explore fluorescence determination of fluazinam in aqueous solution with high sensitivity and selectivity.
Introduction
Fluazinam, a broad-spectrum high-efficiency fungicide, has been widely used in agricultural production [1]. However, excessive application of fluazinam has already affected human’s organic histology and ecological environment. Therefore, it is vital to determine fluazinam in our living environment. Many measurement methods have been developed to analyse fluazinam, including gas chromatography [2], gas chromatography tandem mass spectrometry [3] and high performance liquid chromatography [4]. Although these methods display the advantages of high sensitivity and dependability, they also have some defects of time-consuming, high cost and professional operator. Therefore, the development of green, innovative, convenient, low cost, high selective and sensitive detection methods for fluazinam determination is very crucial.
Metal nanoclusters (MNCs), a new type of fluorescent material, have attracted a lot of attentions owing to their characteristics of strong fluorescence, high quantum-yield, good water solubility and biocompatibility, excellent photostability and stability [5], [6], [7], [8], [9]. So far, MNCs has been applied for bioanalysis, bioimaging, environmental monitoring, industrial catalysis and electronic equipment [10], [11], [12]. Many synthesis means of etching method, electrochemical method, photoreduction method, sonochemical synthesis, microwave assisted method and template assisted synthesis have been developed to prepare MNCs, especially for Cu, Au and Ag nanoclusters [13], [14], [15], [16], [17], [18], [19]. Meanwhile, some protective agents and stabilizers are used to synthesize Cu NCs, including DNAs, protein, polymer and thiols [20], [8], [21], [22]. Cu NCs have been used as high sensitive and selective fluorescent sensors to detect Hg2+ [23], Cd2+ [24], Fe3+ [18], Cu2+ [25], Al3+ [26], ClO− [27], NO2− [28], H2O2 [29], glucose [30], trinitrophenol [31], trinitrotoluene [32] and so on. However, there are few reports of Cu NCs for the detection of fluazinam.
In this work, we prepared the Cu NCs of good water solubility by using polyethyleneimine as a protective agent and hydrazine hydrate as a reducing agent at 95 °C for 12 h. The samples were analysed through UV–visible absorption spectroscopy (UV–vis), fluorescence spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectrometer (XPS). Furthermore, we investigated the effects of storage time, UV irradiation time and concentration of NaCl on the fluorescence intensity of PEI-Cu NCs. More importantly, we established a high sensitive and selective fluorescence detection method for the analysis of fluazinam in environmental water samples.
Section snippets
Apparatus
The fluorescence spectra were recorded on F-7000 fluorescence spectrophotometer (Hitachi, Tokyo Japan) under the voltage of 400 V, in which the Ex/Em slits are 10.0/10.0 nm and the scanning speed is 1200 nm⋅min−1. The UV–vis absorption spectra were obtained by using a Shimadzu 2450 UV–visible spectrophotometer (Shimadzu, Japan). The transmission electron microscopy (TEM) image was acquired by using FEI Tecnai G2 F20 (United States) at an acceleration voltage of 200 kV. X-ray photoelectron
Characterization of the PEI-Cu NCs
To investigate the structure, composition and optical performance of PEI-Cu NCs, the fluorescence spectroscopy, UV–vis absorption spectroscopy, TEM and XPS were employed. As displayed in Fig. 1A, the fluorescence of PEI-Cu NCs demonstrated maximum excitation and emission peaks at 352 and 472 nm, respectively. In addition, the PEI-Cu NCs solutions were light blue under visible light and green under UV light (inset in Fig. 1A). In Fig. 1B, the emission wavelength of PEI-Cu NCs gradually changed
Conclusions
In summary, we synthesized water-soluble fluorescence Cu NCs through a one-pot and simple method. The PEI-Cu NCs had strong fluorescence intensity, excellent water solubility, good stability and high dispersion. To our knowledge, the PEI-Cu NCs was firstly used to detect fluazinam. The detection linear range was 0.5–70 μM and the quenching mechanism might be dynamic quenching and inner filter effect (IFE). In addition, this fluorescence analysis method had been successfully utilized to
CRediT authorship contribution statement
Yuyu Guo: Conceptualization, Methodology, Software, Writing - original draft, Writing - review & editing. Shuxuan Shi: Formal analysis, Investigation. Chunyan Fan: Investigation. Dan Jin: Investigation.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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