Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Fluorescent sensing film decorated with ratiometric probe for visual and recyclable monitoring of Cu2+
Graphical abstract
Introduction
Copper (Cu) plays essential roles in many fundamental physiological processes in the human body including hematopoietic cell growth, enzyme activity, and gene expression [1], [2], [3]. However, the misregulation cellular level of Cu2+ has been proved to be associated with many serious diseases such as cancers, Parkinson’s, Alzheimer’s Menkes and Wilson’s diseases [4], [5], [6]. Meanwhile, Cu2+ contaminations were widely released from the agriculture and industry, which may have become a global challenging problem [7], [8]. Furthermore, the maximum acceptable level of Cu2+ in drinking water was defined as 1.3 ppm (20.0 μM) by the U.S. Environmental Protection Agency [9]. Therefore, it was of great significance to develop reliable and easy-to-use methods to monitor Cu2+ in organisms and the environmental system.
Among various detecting approaches [10], [11], [12], the optical imaging by molecular fluorescent probes have drawn considerable attention due to their high spatial and temporal resolution, easy operation, low cost, and superior sensitivity [13], [14], [15]. A majority of designed fluorescent probes worked in turn-on/turn-off mode, but they were susceptible to external and intrinsic factors such as instruments, pH, temperature, and concentration [16], [17], [18]. Alternatively, the ratiometric method could afford the simultaneous acquisition of the analyte-triggered intensity ratio from two or more measurable emission signals instead of the single emission, which could minimize or eliminate the aforementioned factors [19], [20], [21], [22], [23], [24]. Accordingly, it is still urgently imperative to design and develop ratiometric fluorescent probes for specific and visual monitoring Cu2+ with high sensitivity and accuracy.
Instead of detection in aqueous solution [25], [26], [27], [28], the loading of fluorescence probes on nanofibers/test papers that fixed in the film or on the surface will provide significant potentials for on-site and visual detection [29], [30], [31]. Electrospinning is one of the most effective ways to fabricate various composite nanofibrous film, and have emerged as the smart candidates to construct optical sensing materials with high sensitivity and rapid response due to the high surface area and porosity [32], [33], [34], [35]. However, it is still fraught with difficulties to apply organic fluorescent probe on solid materials such as nanofibrous film as devices for real-time and naked-eye detection.
Based on these considerations, we constructed a ratiometric fluorescent probe that combined the benzoxazole appended xanthenes matrix with an o-hydroxyphenyl unit for tracking Cu2+ concentration under the guidance of theoretical simulation (Fig. 1, Fig. 2). The probe exhibited ideal fluorometric and colorimetric properties and exhibited desirable selectivity to Cu2+ in real water samples, test, strips, and Hela cells. Furthermore, the probe composited fluorescent sensing film was developed by electrospinning for the visual and recyclable monitoring of Cu2+ with superior sensitivity, which provided potentials for the on-site and naked-eye detection in environmental and biological systems.
Section snippets
Materials and measurements
Detailed materials and measurements were shown in the supporting information.
Synthesis of probe BSR
Detailed synthesis was shown in the supporting information.
Preparation of probe BSR-composited nanofibers
The probe BSR (1.00 mg) and polymethyl methacrylate (PMMA Mw 200000, 3.0 g) were dissolved in 7.0 mL DMF at 80 °C for 10 h until it became a homogeneous solution. Then the precursor solution was loaded into a 10 mL gauge needle and was pumped at a flow rate of 0.8 mL/h by a programmable syringe pump. The distance between the needle tip and the collector
Design and synthesis
Before synthesis, we conducted a DFT calculation via Gaussian 09 program [36] to predict the fluorescence and recognition properties of the probe. The basis set of double-z quality [37] (6-31G** for C, H elements, 6–31+G* for N, O, S elements, and DGDZVP for Cu) was used for the construction of molecular models. The vibration analysis showed that all molecular potential energy of the optimized structures was at a local minimum based on the results of vibration analysis without imaginary
Conclusions
In conclusion, we have successfully constructed an effective ratiometric fluorescent probe based on spirolactamized benzothiazole-substituted N,N-diethylrhodol for visual and recyclable detection of Cu2+. Cu2+-induced ESIPT fracture process and the xanthene delocalization would lead to the variation of the fluorescence and colorimetric, which could be recovered by S2−. The probe had been successfully used in real water samples, living Hela cells, and filter paper for the rapid and convenient
CRediT authorship contribution statement
Xilang Jin: Supervision, Project administration, Writing - review & editing. Xuehao Ma: Methodology, Investigation. Wei Zhong: Data curation, Formal analysis. Yixin Cao: Validation, Methodology. Huaqi Zhao: Methodology. Xin Leng: Validation. Jingjing Yang: Methodology. Hongwei Zhou: Supervision. Mengyao She: Supervision.
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.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (No. 21807085 and 21807087), the Technology Innovation Leading Program of Shaanxi (No. 2020TG-031), the Key Research and Development Plan in Shaanxi Province of China (No. 2019KWZ-07), and the Xi’an City Science and Technology Project (No. 2020KJRC0115).
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