Optical Materials 97 (2019) 109396
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Fluorescent sensing platform for the detection of p-nitrophenol based on Cudoped carbon dots
T
Jing Fanga, Shujuan Zhuoa,b,∗, Changqing Zhua,∗∗ a
Anhui Laboratory of Molecule-Based Materials, Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Chemo-Biosensing, School of Chemistry and Materials Science, Anhui Normal University, Wuhu, 241000, PR China b Anhui Meijia New Materials Company Limited, Wuhu, 241000, PR China
A R T I C LE I N FO
A B S T R A C T
Keywords: Cu-doped carbon dots p-Nitrophenol Inner filter effect Fluorescence detection
In this study, we presented a facile strategy to synthesis Cu-doped carbon dots (Cu-CDs) through one-step hydrothermal approach using CuCl2·2H2O and ethanediamine as reaction precursor. Interestingly, the fluorescence of Cu-CDs can be quenched greatly in the presence of p-nitrophenol. Thus, a high selectivity and sensitivity fluorescent sensing platform is constructed for the detection of p-nitrophenol on account of the inner filter effect. Under the optimal condition, the linear detection range is 0.5–50 μM with the detection limit of 0.08 μM (S/ N = 3). This method is successfully applied in quantification of p-nitrophenol in lake water samples, which exhibits potential application prospect.
1. Introduction p-Nitrophenol (p-NP) is a kind of compound widely utilized in fine chemicals. It is used as a raw material or additive for various chemicals, such as pesticides, medicines, dyes, rubber additives, photosensitive materials, and vulcanized materials [1]. However, p-NP can be absorbed by the skin, simultaneously, long-term exposure can stimulate and inhibit the central nervous system and vagal nerve endings, and induce various diseases [2]. Thus, US Environmental Protection Agency (EPA) lists it as a priority pollutant control list [3]. Since p-NP contaminants can cause severe harm to the health of human beings and environment, establishing a rapid, simple, low-cost and sensitive protocol for examining of trace p-NP in environmental samples is of considerable significance [4]. So far, various tools have been developed for the detection of p-NP, including electrochemical [5], phosphorimetric [6], electrocatalytic [7], and colorimetric method [8]. Due to these methods have some defects, such as the preparation process is complex and expensive, which limits their broad use. In contrast, fluorescence analysis displays superiority on account of simplicity, sensitivity and rapidity [9,10]. Consequently, some fluorescent probes or chemosensors have been reported for p-NP assay [11–14]. Carbon dots (CDs) have been widely applied in various fields, for example, energy conversion and storage [15], anticounterfeiting and energyption [16], vivo bioimaging and theranostics [17], neuronal
manipulations [18], sensing [19], fingerprint imaging [20] and photocatalysis [21], owing to unique performance including high stability, good biocompatibility, small sizes, and fascinating photophysi/chemi properties [22]. Although CDs have many excellent properties, their functionality and low fluorescence quantum yield still pose serious challenges [23]. Heteroatom doped carbon and/or other materials have become prevalent means to enhance the performance of these materials [24–34]. Accordingly, heteroatom doping is also a good strategy to improve the fluorescence quantum yield, alter electronic characteristics and endow novel functionalities to the CDs [35,36]. Particularly, metaldoped carbon dots have become a current research focus in virtue of their exceptional optical properties [37–40]. So far, many methods are explored to produce nanomaterials [41–43], including hydrothermal route [44,45], microwave synthesis [46,47], solvothermal reaction [48,49] and high-temperature calcination [50]. Among them, the hydrothermal method has been the most extensively used for its simplicity and environmental friendliness [51]. Simultaneously, the nanomaterials have been widely applied in many fields [52–55], including heavy removal or extract [56–60], supercapacitor [61,62], electromagnetic interference shielding [63], photovoltaic devices [64], anticorrosion [65] and sensing/sensor [66–71]. Herein, we synthesized metal Cu-doped carbon dots (Cu-CDs) via single-step hydrothermal route and designed a simple but effective method to detect p-NP based on Cu-CDs (Scheme 1). This analysis
∗
Corresponding author. Anhui Laboratory of Molecule-Based Materials, Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Chemo-Biosensing, School of Chemistry and Materials Science, Anhui Normal University, Wuhu, 241000, PR China ∗∗ Corresponding author. E-mail addresses:
[email protected] (S. Zhuo),
[email protected] (C. Zhu). https://doi.org/10.1016/j.optmat.2019.109396 Received 28 July 2019; Received in revised form 14 September 2019; Accepted 18 September 2019 0925-3467/ © 2019 Elsevier B.V. All rights reserved.
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Then the solution was diluted to 2 mL with ultrapure water and incubated at room temperature for 2 min to react completely. Afterwards, the fluorescence intensities were measured with the following settings of the spectrofluorimeter: photomultiplier tube voltage, 900 V; excitation and emission band-passes, 10 nm. 2.5. Assay of p-NP in lake water The performance of this probe for assay p-NP in real water samples was studied using the standard addition method. Besides, lake water samples obtained from the lake of Anhui Normal University, and samples were treated according to the previous report [72]. Firstly, the lake water samples were treated by filtration to remove impurities. Then, the lake water samples (10 mL) were centrifuged at 10000 rpm for 20 min to remove the precipitation, and the supernatant was transferred to the filter through a 0.22 μm membrane to further remove impurity substance. Next, 200 μL of the Cu-CDs solutions, 1 mL PBS buffer and different amounts of p-NP were added into volumetric tube sequentially, then 100 μL lake water samples were added. And the mixture was diluted to 2 mL with ultrapure water. After equilibrium for 2 min, the obtained mixture was used for fluorescence determination.
Scheme 1. Preparation of Cu-CDs and the proposed sensing mechanism schematic for p-NP detection.
system exhibited rapid response to p-NP within 2 min. Significantly, the sensing mechanism was proposed that the possible reason was attributed to the inner filter effect (IFE) induced fluorescence quenching of pNP towards Cu-CDs. Notably, the developed method was successfully used for p-NP assay in lake water samples, demonstrating that as-obtained Cu-CDs have great potential for practical application in environmental field. 2. Experimental section 2.1. Chemical and materials
3. Results and discussion
p-Nitrophenol (99%), ethanediamine, lysine (Lys) and glutamic acid (Glc) were obtained from Macklin Biochemical Co. Ltd (Shanghai, China). Copper (II) chloride dihydrate (CuCl2·2H2O) (99%), potassium chloride (KCl), zinc chloride (ZnCl2), ferric chloride (FeCl3) and glucose (Glu) were purchased from Sinopharm (Shanghai, China). Hydroquinone (H2Q), resorcinol, o-aminophenol (OAP), uric acid (UA) and catechol were acquired from Aladdin (Shanghai, China). Phosphate buffer (PBS, 0.1 M) was prepared by mixing solutions of Na2HPO4·12H2O and NaH2PO4·2H2O. All other reagents were of analytical grade and no need to be further purification when using. Ultrapure water (18.2 MΩ cm) was used throughout.
3.1. Characterization of the Cu-CDs The Cu-CDs can be obtained through a one-pot hydrothermal route. As shown in Fig. 1a, transmission electron microscopy (TEM) image confirmed the morphology of the Cu-CDs. It indicates that the shape of the as-prepared Cu-CDs is spherical and reveals that the Cu-CDs possess a good monodispersity and narrow size distribution, the diameter of the obtained Cu-CDs ranged between 1 and 3 nm, with an average diameter of 1.8 nm (Fig. 1b). The high resolution TEM (HRTEM) image (inset in Fig. 1a) displays an interplanar spacing of about 0.23 nm, which is similar to that of (100) lattice plane of graphitic carbon, indicating the crystalline nature of Cu-CDs. The effects of pH, ionic strengths and UV exposure on the stability of the Cu-CDs were measured and presented in Fig. 2. The fluorescence intensity of Cu-CDs gradually increase with pH increment from 5 to 12 (Fig. 2a), while the intensity displays negligible change after irradiated under UV light (365 nm) for 60 min (Fig. 2b), indicating their excellent photo-stability. Additionally, Cu-CDs maintain stable fluorescence intensities even the concentration of NaCl reaching as high as 1 M (Fig. 2c). The chemical composition and structure were further characterized by FTIR spectrum. As can be seen from Fig. 3a, the characteristic absorption peak around 3448 cm−1 is attributed to the stretching vibration of O–H group. The peak located at 2861 cm−1 is ascribed to the stretching vibration of C–H bond. The peak centered at 1595 cm−1 stems from the C]C stretching vibration. The peak appeared at 1454 and 1361 cm−1 could be identified as C–N and C–O groups [73], indicating that nitrogen and oxygen-containing groups are presence on the surface of CDs, which imparts high water-solubility to CDs.
2.2. Instruments Fluorescence study was conducted on a FS5 Fluorescence Spectrophotometer. X-ray photoelectron spectroscopy (XPS) data were collected using an ESCALAB 250XI electron spectrometer (Thermo, USA). Transmission electron microscopy (TEM) was carried out on a HT-7700 (Tokyo, Japan). Fourier transform infrared (FTIR) spectrum was recorded using a PerkinElmer FTIR spectrophotometer (PE-983, USA) using KBr pellet at room temperature. UV–Vis absorption spectra were measured from a U-2910 spectrophotometer (Hitachi, Japan). 2.3. Preparation of Cu-doped CDs The Cu-CDs were prepared by one-step hydrothermal treatment of ethanediamine and CuCl2·2H2O as reaction precursor. Briefly, 1 mL ethanediamine and 0.1 g CuCl2·2H2O were dissolved in 29 mL of ultrapure water under bath sonication for 5 min. Following the mixture solution was transferred into a 50 mL Teflon-equipped stainless steel autoclave, the reaction system was sealed and heated at 180 °C for 10 h. After the obtained solution was cooled down to room temperature naturally, the products were collected by centrifuging. Finally, the obtained Cu-CDs solution was purified using a dialysis bag (MWCO 1000) for 24 h to remove the impurities. After purification, the Cu-CDs aqueous solution was stored at 4 °C before use. 2.4. Fluorescence analysis of p-NP A fluorescence assay for p-NP under the following procedures. Briefly, 200 μL of the Cu-CDs solutions was put into 1 mL of PBS (0.1 M, pH 11), followed by the addition of different concentrations of p-NP.
Fig. 1. (a) TEM and HRTEM (inset) images of the Cu-CDs. (b) The corresponding particles size distribution. 2
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Fig. 2. Fluorescence intensity variations of the Cu-CDs as a function of (a) pH, (b) UV exposure and (c) concentration of NaCl.
The full XPS survey spectrum of the Cu-CDs clearly shows four peaks at 285.1, 401, 532.1 and 935.1 eV (Fig. 3b), which are attributed to C 1s, N 1s, O 1s and Cu 2p, respectively. And the corresponding content of each element is C 50.56%, N 11.73%, O 36.2% and Cu 1.51% (At%). The appearance of the C 1s peak (Fig. 4a) at 284.6, 285.1 and 285.9 eV, are ascribed to C–C/C]C, C–N and C–O [74], respectively. Additionally, the N 1s spectrum exhibits three peaks at 399.5, 400.1 and 406.6 eV (Fig. 4b) that may be assigned to C–N–C, C–N/N–H and NO3 groups [75,76]. The high resolution O 1s spectrum in Fig. 4c could be deconvoluted into two peaks, locating at 531.9 and 532.6 eV, which are belong to C–O and C]O/N]O groups [77]. The Cu 2p spectrum (Fig. 4d) displays that the metal copper doped into CDs successfully. There exists two main peaks at 934.8 and 954.7 eV, which is likely classified to Cu 2p3/2 and Cu 2p1/2 bonding orbitals [78]. 3.2. Optical properties of Cu-CDs The UV–Vis absorption and fluorescence spectra of Cu-CDs were depicted in Fig. 5a. The absorption spectrum of the Cu-CDs exhibited two absorption peaks around at 227 and 318 nm, which may be assigned to the π-π* transition of aromatic sp2 domain and n-π* transition of C]O [79]. Meanwhile, the Cu-CDs show a maximum emission at 380 nm with excitation wavelength at 320 nm. Moreover, excitationdependent behavior of Cu-CDs was also observed (Fig. 5b), which likely attributed to the existence of different-size nanodots and considerable of emissive traps sites on the Cu-CDs surface [80]. The fluorescence quantum yield of the Cu-CDs is 7.8% (quinine sulfate as a reference).
Fig. 4. High-resolution XPS spectra of (a) C 1s, (b) N 1s, (c) O 1s and (d) Cu 2p of the Cu-CDs.
at higher pH. The experimental results show that pH 11 was the optimum value. Therefore, pH 11 was selected for sensing system. The incubation time was optimized in Fig. 6b. Upon the addition of p-NP, the fluorescence intensity of Cu-CDs decreased rapidly with time and become slowly after 2 min. Thus, 2 min was chosen for the sensing.
3.3. Optimization of experimental conditions 3.4. Fluorescence assay for p-NP
To obtain excellent sensing performance of Cu-CDs, we evaluated critical analytical parameters, including pH and reaction time. As we all known, pH values of the buffer is a key factor for the reacting system. As presented in Fig. 6a, the fluorescence intensity of Cu-CDs progressively raise in selected pH range. Addition of p-NP led to fluorescence quenching in the whole pH range and quenching extent was enhanced
Cu-CDs are expected to be ideal candidate to detect p-NP under the optimum conditions. When adding different amounts p-NP into Cu-CDs solution, the response of Cu-CDs fluorescence was illustrated in Fig. 7a. As can be seen that the fluorescence intensity of Cu-CDs decreases
Fig. 3. (a) FT-IR spectrum and (b) XPS full scan of Cu-CDs. 3
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Fig. 5. (a) UV–Vis absorption and fluorescence spectra of Cu-CDs. (b) Excitation-dependent emission of Cu-CDs.
Fig. 6. (a) Fluorescence response of the proposed method at different pH values. (b) Time-dependent fluorescence response of the sensing system. The concentration of p-NP is 50 μM. The error bar represents the standard deviation for three determinations. Fig. 7. (a) The fluorescence emission spectra with increasing p-NP concentration, p-NP concentration was 0, 0.5, 1, 5, 10, 20, 45 and 50 μM (from top to bottom), respectively. (b) The calibration curve of pNP obtained with Cu-CDs. F0 and F are the intensity of the Cu-CDs in the absence and presence of p-NP. The error bars mean the standard deviation of three assays.
3.5. Possible sensing mechanism of Cu-CDs to p-NP
Table 1 Comparison of analytical performance for p-NP sensing using fluorescent methods. Materials
Linear range (μM)
LOD (μM)
Refs.
MIP-capped CdTe QDs B,N-CDs Cr-CDs NCDs Amine-CQDs@UiO-66 PCDs Cu-CDs
1–30 0.5–60 0.8–150 0.1–100 0.01–20 0.5–60 0.5–50
0.04 0.2 0.27 0.017 0.0035 0.26 0.08
[81] [82] [83] [84] [85] [86] This work
Fig. 8a reveals that there is a substantial wide overlap between the absorption spectrum of p-NP and the emission spectrum of the Cu-CDs. The result indicates the possibility of IFE process occurred between the Cu-CDs and p-NP. Moreover, Fig. 8b shows the fluorescence lifetime profiles of the Cu-CDs alone and mixture of the Cu-CDs and p-NP. We can see that the fluorescence lifetime is almost unchanged with the addition of p-NP. To further explore the detection mechanism for p-NP, the UV–Vis absorption spectra of Cu-CDs, p-NP and Cu-CDs + p-NP system were measured. As described in Fig. 8c, compared with the absorption spectrum of p-NP alone, no new absorption peak appeared upon addition of Cu-CDs, indicating that no ground state complexes are formed between Cu-CDs and p-NP. By combination of larger spectral overlap and invariant fluorescence lifetime, the possible quenching mechanism of p-NP towards Cu-CDs was ascribed to IFE [87,88].
gradually with increment of p-NP. The linear detection range is 0.5–50 μM with the limit of detection (LOD) as low as 0.08 μM (R2 = 0.998, Fig. 7b). Additionally, the sensing performance is comparable to those of other fluorescent analytical methods, as summarized in Table 1.
4
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Fig. 8. (a) The UV–Vis absorption spectrum of p-NP and the fluorescence emission spectrum for Cu-CDs. (b) The fluorescence decay curves of Cu-CDs in the absence and presence of p-NP. (c) UV–Vis absorption spectra of Cu-CDs, p-NP and Cu-CDs + p-NP system.
4. Conclusions In summary, a facile and green synthesis route has developed for preparation of fluorescent Cu-CDs. Moreover, a high selectivity and sensitivity sensing platform was constructed to detection p-NP based on Cu-CDs probe. The possible mechanism for the fluorescence sensing was attributed to inner filter effect of p-NP towards Cu-CDs. Importantly, the proposed sensing strategy is successfully applied to the detection of pNP in lake water samples, demonstrating potential application in environmental monitoring. Declaration of competing interest Fig. 9. The fluorescence response of the Cu-CDs in the presence of 40 μM different species. F0 and F are the intensity of the Cu-CDs in the absence and presence of interferent.
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.
Table 2 Detection of p-NP in lake water samples. Samples
1
2
3
Acknowledgments
Spiked (μM)
Found (μM)
Recovery (%)
3 3 3 20 20 20 45 45 45
2.94 3.07 3.08 20.96 20.4 19.8 46.8 45.9 44.5
98 102 103 105 102 99 104 102 98.9
RSD (%)
2.6
This work was supported by Anhui Laboratory of Molecule-Based Materials Open Fund (No. fzj19006) and National Natural Science Foundation of China (Nos. 21303003 and 21375003).
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3.6. Selectivity detection for p-NP The selectivity of method is an vital parameter. So, various common substances, including several substances with similar structure to p-NP, amino acids, and different ions were investigated. As described in Fig. 9, the fluorescence of the Cu-CDs was quenched significantly on the addition of p-NP compared with other interfering species, namely, other substance have little effect on the fluorescence of the Cu-CDs at the same concentration, indicating that Cu-CDs possess excellent selectivity for assay of p-NP.
3.7. Application of the p-NP detection method in water samples To evaluate the potential application of the Cu-CDs, we used the CuCDs based fluorescence sensing platform for detection of p-NP quantitatively in real lake water samples. As displayed in Table 2, it was found that the observed values were consistent with those of the added p-NP with relative standard deviation (RSD) within 2.5–2.8%. In addition, the satisfactory recoveries of the real samples were 98–105%. These results show that the method has a good application prospect in the field of environmental assessment. 5
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