One-pot fabrication of FRET-based fluorescent probe for detecting copper ion and sulfide anion in 100% aqueous media

Accepted Manuscript One-pot fabrication of FRET-based fluorescent probe for detecting copper ion and sulfide anion in 100% aqueous media

Kun Lv, Jian Chen, Hong Wang, Peisheng Zhang, Maolin Yu, Yunfei Long, Pinggui Yi PII: DOI: Reference:

S1386-1425(17)30042-2 doi: 10.1016/j.saa.2017.01.031 SAA 14884

To appear in:

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Received date: Revised date: Accepted date:

26 August 2016 8 January 2017 16 January 2017

Please cite this article as: Kun Lv, Jian Chen, Hong Wang, Peisheng Zhang, Maolin Yu, Yunfei Long, Pinggui Yi , One-pot fabrication of FRET-based fluorescent probe for detecting copper ion and sulfide anion in 100% aqueous media. The address for the corresponding author was captured as affiliation for all authors. Please check if appropriate. Saa(2017), doi: 10.1016/j.saa.2017.01.031

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ACCEPTED MANUSCRIPT One-pot fabrication of FRET-based fluorescent probe for detecting copper ion and sulfide anion in 100% aqueous media Kun Lv, Jian Chen*, Hong Wang, Peisheng Zhang*, Maolin Yu, Yunfei Long and Pinggui Yi

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Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of

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Ministry of Education, Hunan Provincial Key Laboratory of Controllable Preparation

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and Functional Application of Fine Polymers, Hunan Province College Key

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Laboratory of QSAR/QSPR, Institute of Functional Materials, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan,

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Hunan 411201, China.

* Corresponding author. Tel.: +86 731 58290045; fax: +86 731 58290045.

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E-mail: [email protected] (J. Chen); [email protected] (P. S. Zhang);

Abstract

The design of effective tools for detecting copper ion (Cu2+) and sulfide anion (S2−) is of great

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importance due to the abnormal level of Cu2+ and S2− has been associated with an increase in risk of many diseases. Herein, we report on the fabrication of fluorescence

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resonance energy transfer (FRET) based fluorescent probe PF (PEI-FITC) for detecting Cu2+ and S2− in 100% aqueous media via a facile one-pot method by covalent linking fluorescein isothiocyanate (FITC) with branched-polyethylenimine (b-PEI). PF could selectively coordinate with Cu2+ among 10 metal ions to form PF-Cu2+ complex, resulting in fluorescence quenching through FRET mechanism. Furthermore, the in situ generated PF-Cu2+ complex can be used to selectively detect S2− based on the displacement approach, resulting in an off-on type sensing. There is no obvious interference from other anions, such as Cl-, NO3-, ClO4-, SO42-, HCO3-, CO32-, Br-, HPO42-, F- and S2O32-. In addition, PF was

successfully used to determine Cu2+ and S2− in human serum and tap water samples.

ACCEPTED MANUSCRIPT Therefore, the FRET-based probe PF may provide a new method for selective detection of multifarious analysts in biological and environmental applications, and even hold promise for application in more complicated systems.

Keywords: copper ion, sulfide anion, FITC, fluorescence quenching, FRET

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1. Introduction Recently, the development of selective and efficient fluorescent probes for

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anion detection has attracted continuous attention due to their promising application in biological, industrial and environmental monitoring.[1-9] Sulfide

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anion (S2−), as one type of biologically and environmentally important anions, is extensively utilized in industrial processes including sulfur and sulfuric acid

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production, dyes and cosmetic manufacturing, etc.[10-12] It is also a toxic traditional pollutant that can be generated from industrial processes and

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biological metablism.[13-15] Moreover, its protonated form, HS- and H2S become even more toxic than S2− self, [16,17] and abnormal levels of S2− are

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involved in a variety of diseases, such as hypertension, liver cirrhosis, diabetes

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and Alzheimer's disease.[18-24] Thus, to better understand the biological functions of S2−, development of highly selective and sensitive fluorescent probes for detecting S2− is urgently required.

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So far, a large number of fluorescent probes for detecting S2− have been conducted mainly based on three strategies, such as (a) reduction of azides to

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amines,[25-27]

(b)

nucleophilic

addition[28-31],

(c)

copper

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precipitation[32-34] and (d) a coordinative-based approach [35-39]. For fluorescent probes based on reduction (a), addition (b) and coordinative-based (d) strategies, the reactions are relatively slow and irreversible. In contrast, fluorescent probes based on CuS precipitation strategy have been highly concerned due to their extremely fast recognition process. In addition, there are two outstanding properties: one is the fast kinetics of precipitation of CuS; another one is the corresponding quite low-solubility constant (ksp =

ACCEPTED MANUSCRIPT 6.3×10-36).[40] In view of these advantages, a variety of fluorescent probes for S2− detection using CuS precipitation strategy have been reported.[41-43] However, most of them can only work in organic co-solvents media, which would significantly limit their practical applications in physiological condition and environmental systems. Despite of several examples can detect S2− in 100%

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aqueous media, they generally requires complicated synthesis pathway and exhibits poor photostability.[44-48] Therefore, it is desirable to develop robust

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fluorescent probes for detecting S2− that are simple, fast-responding and water soluble.

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With these factors in mind, herein, we report a facile one-pot method for designing a novel fluorescence probe PF for reversible sensing of Cu2+ and S2−

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in 100% aqueous media via fluorescence resonance energy transfer (FRET) mechanism. In this probe, branched-polyethylenimine (b-PEI) can not only

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improve the solubility of PF in water, but also facilitate enhanced binding affinity for Cu2+. As shown in scheme 1, the probe PF could firmly bind Cu2+

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to form stable complex PF-Cu2+, leading to an obvious fluorescence quenching

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due to the FRET effect. Upon addition of S2−, its fluorescence recovers quickly on the basis of formed CuS. Moreover, this probe exhibits several satisfactory advantages including high selectivity, good reversibility and outstanding

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long-term photostability. Details about the synthesis of the fluorescent probe PF and its characterization data are presented in the supporting information

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(Figure S1 and Figure S2).

ACCEPTED MANUSCRIPT Scheme 1. Schematic presentation of novel probe PF for selectively recognizing Cu 2+ and S2−.

2. Experiment 2.1 Apparatus. UV-vis

spectra

were

recorded

on

a

Shimadzu

UV-2501PC

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spectrophotometer at room temperature. Fluorescence spectra were obtained through an Edinburgh FLS920 at room temperature. The 1H NMR spectra was

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measured on a Bruker AV-II 500 MHz NMR spectrometer.

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2.2 Reagents.

Fluorescein isothiocyanate (FITC, 99.5%) and branched-polyethylenimine

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(average molecular weight around 10000, b-PEI 10000) were obtained from Aldrich and used as received. Nitrate salts of metal ions (Cu2+, Mg2+, Ca2+, Fe2+,

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Zn2+, Mn2+, Na+, Ni2+, K+, Pb2+ and Hg2+) and sodium salts of anions (S2-, Cl-, NO3-, ClO4-, SO42-, HCO3-, CO32-, Br-, HPO42-, F- and S2O32-) were of analytic grade. The water used herein was the double-distilled water upon being treated by ion

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exchange columns and then by a Milli-Q water purification system. All the other

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reagents and solvents were purchased commercially and used without further purification unless noted otherwise.

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2.3 Synthesis of the PF

Branched-polyethylenimine (average molecular weight around 10000) (0.1

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g, 0.01 mmol) and fluorescein isothiocyanate (2 mg, 0.005 mmol) were dissolved in a flask with 10 mL water. The mixture was stirred at room temperature for 2 days. Subsequently, the unreacted fluorescein isothiocyanate was removed by dialysis through a permeable membrane (MWCO 3500) against water. Afterwards the water was evaporated under reduced pressure and the product (the probe PF) was obtained as a yellow solid. As shown in the Figure S2 (Supplementary Materials), 1H NMR (D2O, 500 MHz) ppm: 1.0-3.5 (protons of PEI), 6.3-7.7 (fluorescein aromatic protons). 2.4. General Procedure for Cu2+ and S2- detection

ACCEPTED MANUSCRIPT Double-distilled water was used through all spectroscopic tests. Unless otherwise stated, all the fluorescence measurements were performed in 10 mM PBS buffered (pH 7.0) water solution, according to the following procedure. For Cu2+ detection, in a 5 mL cuvette, 2 mL probe (PF; solid content: 0.03 wt%) contained PBS buffer solution was prepared in a cuvette, followed by addition of an appropriate volume of

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stock solution of Cu2+ (0-110 μM). The final volume of liquid in the cuvette was adjusted to 3.0 mL with PBS. After incubated at room temperature for 5 minutes, the

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fluorescence of the probe sample was measured on an Edinburgh FLS920. At the same time, a blank solution without Cu2+ was prepared and measured under the same

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conditions as a reference. For S2- detection, in a 5 mL cuvette, 2 mL probe (PF; solid content: 0.03 wt%) contained PBS buffer solution pretreated with 80 μM Cu2+ was

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prepared in a cuvette, followed by addition of an appropriate volume of stock solution of S2- (0-100 μM). The final volume of liquid in the cuvette was adjusted to 3.0 mL

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with PBS. After incubated at room temperature for 5 minutes, the fluorescence of the probe sample was measured on an Edinburgh FLS920. Fluorescence spectral

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parameters were set as: λex = 490 nm, λem = 521 nm, Slit width: Ex = 1.7 nm, Em = 1.7

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nm. 3 Results and discussion

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3.1. Fluorescent response of the probe PF toward Cu2+ and S2Firstly, the fluorescence titrations spectra of PF towards Cu2+ were

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investigated in 100% phosphate buffer saline (PBS) water (10 mM, pH 7.0), as shown in Figure 1A. It can be seen that the free probe PF exhibited strong emission peak at 521 nm. With gradually addition of Cu2+ (0-110 μM), the fluorescence peak at 521 nm was quenched immediately, while no obvious fluorescent changes of free FITC molecules in PBS aqueous solution can be observed in the presence of Cu2+ (80 μM) or S2- (50 μM) (Figure S3). Evidently, the phenomena may be ascribed to FRET effect between FITC (donor) and PEI-Cu2+ complex (acceptor). And then, the time course of the response of PF towards Cu2+ was also monitored, the results showed that the chelation between

ACCEPTED MANUSCRIPT PF and Cu2+ accomplished within 60 s (Figure S6) (Supplementary Materials), indicating that the probe PF performed an excellent rapid response to Cu2+. In addition, a good linear relationship between the fluorescence signal changes (1-I/I0) and the Cu2+ concentration in the range of 0 μM to 60 μM is obtained (Figure 1B), and the calculated detection limit is 1.0 μM, which can completely satisfy the standard when detect the Cu2+ in the blood system (15.7-23.6 μM)

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and Cu2+ detection in drinking water under the American Environmental

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Protection Agency limit (20 μM).[49]

Subsequently, the selectivity of the probe (PF) for Cu2+ was evaluated in the

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presence of various competitive and transition metal cations like Mg2+, Ca2+, Fe2+, Zn2+, Mn2+, Na+, Ni2+, K+, Pb2+ and Hg2+. As exhibited in Figure 1C, with addition of

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Cu2+, the fluorescence signal changes (1-I/I0) for the PF were dramatically enhanced. However, other putative interferents displayed little influence on the fluorescent

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signal changes (1-I/I0) of PF. These results suggested that PF exhibited high selectivity for the detection of Cu2+ over other putative interferents. Moreover, the

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effects of some coexisting cations on Cu2+ sensing were also performed, as depicted

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in Figure 1D, Various coexisting ions displayed a negligible influence on the recognition of Cu2+, indicating that PF can be served as a potential candidate

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for selectively detecting Cu2+ in some complicated matrix.

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Figure 1. (A) Fluorescence spectra of the probe PF (content: 0.03 wt%) upon addition of Cu 2+ with different concentrations (0-110 μM); (B) The linear relationship between the fluorescence intensity

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changes (1-I/I0) and the concentration of Cu 2+; (C) Fluorescence intensity changes (1-I/I0) of PF in the presence of 100 μM Cu 2+ and 100 μM of various metal ions; (D) Fluorescence intensity ratios (I/I0) of PF in the presence of 100 μM Cu 2+ and 100 μM of various coexisting metal ions; BLK is only 100 μM Cu 2+.

It has been well documented that S2- can quickly react with Cu2+ to form a

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stable CuS precipitation with low-solubility (Ksp = 6.3×10−36), and thereby conduce the recovery of the quenched fluorescence.[50] Based on this idea, a fluorescence assay was conducted to explore the quantitative analysis of

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PF-Cu2+ complex ensemble toward S2-. As shown in Figure 2A, in the absence of S2−, the fluorescence signal of PF-Cu2+ complex ensemble is rather weak,

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and the fluorescence signal is gradually enhanced with increasing concentration of S2− (0-100 μM). Moreover, there is a good linear relationship between the fluorescence signal ratios (I/I0) and the S2− concentration in the range of 10 μM to 100 μM (Figure 2B), and the calculated detection limit is 1.2 μM, which is lower than the maximum recommended S2− concentration (about 500 μg/L or 15 μM) in drinking water by World Health Organization.[44] In addition, the response time of the PF-Cu2+ complex towards S2− can be completed within 55 s (Figure S7) (Supplementary Materials), implying that the PF-Cu2+ complex showed a fast response to S2-.

ACCEPTED MANUSCRIPT Figure 2C displayed the selectivity of PF-Cu2+ complex to S2− in the presence of some other anions including Cl-, NO3-, ClO4-, SO42-, HCO3-, CO32-, Br-, HPO42-, F- and S2O32-. As seen from that only S2− could induce an obvious fluorescence enhancement, whereas other anions resulted in almost no fluorescence change. Moreover, the interference of other anions coexisting with S2- was also studied (Figure 2D). Obviously, coexistence of these anions

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displayed little interference on the fluorescence enhancement of PF-Cu2+

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complex system, suggesting that the system can be used to highly selectively detecting S2- in some complicated systems, such as environmental and

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biological systems.

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Figure 2. (A) Fluorescence spectra of PF-Cu2+ (adding 80 μM of Cu 2+ to dilute PF solution, content: 0.03 wt%) upon addition of Na2S ([Na2S]= 0-100 μM); (B) The linear relationship between the fluorescence intensity ratios (I/I0) and the concentration of S 2−; (C) Fluorescence intensity ratios (I/I 0) of PF-Cu2+ (adding 80 μM of Cu2+ to dilute PF solution) in the presence of 100 μM S 2− and 100 μM of various anions; (D) Fluorescence intensity ratios (I/I 0) of PF-Cu2+ in the presence of 100 μM S 2− and 100 μM of various coexisting anions; BLK is only 100 μM S 2−.

3.2. The mechanism of PF for sensing Cu2+ and S2It has been well documented that multi-amine contained compound (for example PEI) can coordinate with Cu2+ to form the Cu2+ complexes (acceptor), thereby

ACCEPTED MANUSCRIPT quenching the fluorescence of fluorogen (donor) as a result of fluorescence resonance energy transfer (FRET) mechanism [39,46]. As presented in Figure S4 (Supplementary Materials), an obvious broad absorption band ranging from 470 to 800 nm can be observed after the b-PEI treated with Cu2+. However, no obvious absorption band can be seen from 470 to 800 nm in the presence of free Cu2+ or b-PEI aqueous solution, respectively. In addition, there was an obvious spectral overlap

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between the emission band of FITC (donor) and the absorption band of the Cu2+

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complexes (acceptor) (Figure S5), and the FRET process could be occurred from the FITC (donor) to the Cu2+ complexes (acceptor), leading to a decline in fluorescence

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intensity of FITC. In the presence of S2-, the S2- can react with Cu2+ in aqueous media to form a stable CuS species with low-solubility (Ksp = 6.3×10-36). Thus, with addition

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of S2- into PF-Cu2+ system, the fluorescence intensity of FITC recovered due to the inhibitation of FRET process (Figure S5). To further study the FRET process,

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fluorescence lifetimes have been recorded, as depicted in Figure 3. The lifetime of FITC in PF decreased after addition of Cu2+, while no obvious lifetime changes of

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free FITC can be observed after addition of Cu2+. The change lifetime of the donor

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directly certifies the occurrence of FRET process.

Figure 3. (A) Fluorescence decay curves of PF sample at 521 nm before and after addition of Cu 2+, as well as further introduction of S 2− (solid content: 0.03 wt%, [Cu 2+] = 20 μM, [S2-] = 20 μM, λex = 490 nm); (B) Fluorescence decay curves of FITC sample at 521 nm before and after addition of Cu 2+, as well as further introduction of S2− (Concentration of FITC: 5 μM, [Cu2+] = 20 μM, [S2-] = 20 μM, λex = 490 nm).

3.3. The reversible switching property of PF The reversible switching property of PF was further tested by alternatively adding of Cu2+ (100 μM) and S2− (100 μM). As presented in Figure 4, the

ACCEPTED MANUSCRIPT fluorescence signal (521 nm) of PF descended firstly with Cu2+ and subsequently elevated upon addition of S2−. Such a reversible cycle could be repeated at least for six times by the alternate change of Cu2+ and S2− addition, indicating that PF held good reversibly switchable sensing nature, and was an ideal fluorescence probe for reversibly monitoring the interconversion of the

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Cu2+ and S2−.

Figure 4. Switching cycles of PF upon alternative addition of Cu 2+ (100 μM) and S2− (100 μM) (solid

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content: 0.03 wt%, λex= 490 nm, λem= 521 nm).

3.4. The long-term fluorescence stability of PF

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In addition, the long-term fluorescence stability of PF for Cu2+ and

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PF-Cu2+ complex for S2− was measured, as presented in Figure 5. The result demonstrates that less than 1% of the initial fluorescence signal ratios was lost after storing for a long time (over 50 days), revealing that the excellent long-term fluorescence stability of PF for sensing Cu2+ and S2-.

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Figure 5. (A) Long-term fluorescence stability of PF for Cu2+ recognition (solid content: 0.03 wt%, Cu 2+ concentration: 100 μM); (B) long-term fluorescence stability of PF-Cu2+ complex for S2- recognition

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(solid content: 0.03 wt%, Cu 2+ concentration: 80 μM, S2- concentration: 100 μM) ; λex = 490 nm, λem =

3.5. Investigation of pH-dependence

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521 nm.

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The pH effect on the performance of the probe PF towards Cu2+ and S2- is investigated, as shown in Figure 6. In the absence of Cu2+, the fluorescence intensity (I521) of PF dispersion was increased regularly with the increasing of pH (4.0-10.0). In

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the presence of Cu2+, a remarkable decrease of fluorescence intensity (I521) was

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observed. It can also be found that the PF exhibited relative placid fluctuation from pH 4.0 to 10.0. And as revealed in Figure 4B, the fluorescence intensity (I521) of PF-Cu2+ dispersion without S2- was also increased regularly with the increasing of pH

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( 4.0-10.0), a remarkable recovery of fluorescence intensity (I521) was appeared. These

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results confirmed that the PF could act as excellent fluorescent sensor for Cu2+ and S2in physiological condition.

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Figure 6. (A) pH-dependence of the fluorescent response of PF for Cu2+ (solid content: 0.03 wt%, Cu 2+

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concentration: 80 μM, λ ex = 490 nm, λem = 521 nm); (B) pH-dependence of the fluorescent response of PF-Cu2+ for S2- recognition (solid content: 0.03 wt%, Cu 2+ concentration: 80 μM, S2- concentration: 100

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μM, λex = 490 nm, λem = 521 nm).

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3.6. Determination of Cu2+ and S2- in real sample

To study the practical application in some complicated systems, we made an

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attempt to evaluate whether the probe could effectively determine Cu2+ and S2- in human serum and tap water samples. In this study, different concentrations of Cu2+

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and S2- were added to the serum samples and tap water, a good recovery was observed.

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As presented in Table 1 and Table 2, the recoveries are in range of 92.0% to 102.0%, which implied an outstanding performance of the probe for accurately sensing Cu2+

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and S2- in human serum and tap water samples.

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Table 1. Determination of Cu2+ in human serum and tap water. Added amount Found amount Sample RSD (n =3, %) of Cu2+ (μM) of Cu2+ (μM) 5.00 4.60 0.33 human serum 20.00 20.50 0.15 50.00 48.97 0.29

tap water

5.00 20.00 50.00

4.62 18.82 47.23

0.26 0.32 0.18

Recovery (%) 92.00 102.50 97.94 92.40 94.10 94.46

ACCEPTED MANUSCRIPT Table 2. Determination of S2- in human serum and tap water. Added amount Found amount Sample RSD (n = 3, %) of S2- (μM) of S2- (μM) 10.00 9.54 0.13 human serum 40.00 38.20 0.25 80.00 77.43 0.23 0.30 0.17 0.28

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tap water

9.66 38.62 78.67

95.40 95.50 96.78 96.60 96.55 98.33

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10.00 40.00 80.00

Recovery (%)

4. Conclusion

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In conclusion, we have successfully developed a FRET-based fluorescent

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probe PF for reversibly detecting Cu2+ and S2- in water by using a facile one-step method. The as-prepared fluorescent probe PF presented high selectivity, rapid

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time response, good reversibility and excellent long-term fluorescence stability (>50 days). Moreover, the probe PF can also be further used for the selective detection of Cu2+ and S2- in human serum and tap water samples. We expect that the

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probe PF can enlarge its potential applications in physiological and

Acknowledgements

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environmental systems for Cu2+ and S2- detection in the future.

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We gratefully acknowledge financial support of the present work by NSFC (Project no. 51373002 and 51603067), Scientific Research Foundation for the

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Returned Overseas Chinese Scholars, Open Project Program of Key Laboratory for High Performance and Functional Polymer Materials of Guangdong province (South China University of Technology) (Project no. 20160005), and Open Project Program of State Key Laboratory of Chemo/Biosensingand Chemometrics (Project no. 2013008).

Reference [1] Tang, Y. H.; Lee, D. Y.; Wang, J. L.; Li, G. H.; Yu, J. H.; Lin, W. Y.; Yoon, J. Y. ChemInform abstract: development of fluorescent probes based on

ACCEPTED MANUSCRIPT

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protection-deprotection of the key functional groups for biological imaging. Chemical Society Reviews 2015, 46(36), 5003-5015. [2] Zhang, X.; Yin, J.; Yoon, J. Recent advances in development of chiral fluorescent and colorimetric probes. Chemical Reviews 2014, 114(9), 4918-4959. [3] Liu, G.; Zhao, L. M. A simple colorimetric and on-off fluorescent chemoprobe for biologically important anions based on thiourea droups. Spectroscopy Letters 2012, 45(45), 424-429. [4] Liu, J. M.; Song, Z. H. Determination of total chromium in biological samples by automated reagent injection chemiluminescence analysis. Analytical Letters 2013, 46(11), 1804-1815. [5] Saikia, G.; Dwived,i A. K.; Iyer, P. K. Development of solution, film and membrane based fluorescent probe for the detection of fluoride anions from water. Anal Methods 2012, 10(10), 3180-3186. [6] Ding, Z.; Liu, J.; Lin, R.; Hou, X. H. Near infrared fluorescent trypsin stabilized gold nanoclusters as surface plasmon enhanced energy transfer bioprobe and in vivo cancer imaging bioprobe. Analytical Chemistry 2013, 85(6), 3238-3245. [7] Lohar, S.; Sahana, A.; Banerjee, A.; Banik, A.; Mukhopadhyay, S. K.; Matalobos, J. S.; Das, D, Antipyrine based arsenate selective fluorescent probe for living cell imaging. Analytical Chemistry 2013, 85(3), 1778-1783. [8] Wang, Q. M.; Gao, W.; Li, Y.; Yang, T. T.; Ju, Y.; Tang, X. H. Highly sensitive and selective fluorescent “turn-on” probe for determination of aluminum ion in aqueous solution. Spectroscopy Letters 2015, 49(3), 459-492. [9] Wang, X. H.; Guo, Z. Q.; Zhu, S. Q.; Liu, Y. J.; Shi, P.; Tian, H.; Zhu, W. H. Rational design of novel near-infrared fluorescent DCM derivatives and their application in bioimaging. Journal of Materials Chemistry B 2016, 4, 4683-4689. [10] Jiang, J. J.; Chan, A.; Ali, S.; Saha, A.; Haushalter, K. J. Hydrogen Sulfide-Mechanisms of toxicity and development of an antidote. Scientific Reports 2016, 6, 20831-20840; [11] Forte,E.; Borisov,V. B.; Falabella, M.; Colaço, H. G.; Trejo, M. T. The terminal oxidase cytochromebd promotes sulfide-resistant bacterial respiration and growth. Scientific Reports 2016, 6, 23788-23795. [12] J. M. Kang, Z. Li, C. L. Organ, C. M. Park, C. T. Yang, A. Pacheco, D. F. Wang, D. J. Lefer, and M. Xian, pH-Controlled hydrogen sulfide release for myocardial ischemia-reperfusion injury. Journal of the American Chemical Society 2016, 138(20), 6336-6339. [13] Singha, S.; Kim, D.; Moon, H.; Wang, T.; Kim, K. H.; Shin, Y. H.; Jung, J. y.; Seo, E.; Lee, S. J.; Ahn, K. H. Toward a selective, sensitive, fast-responsive, and biocompatible two-photon probe for hydrogen sulfide in live cells. Analytical Chemistry 2015, 87(2), 1188-1195; [14] Hai, Z. J.; Bao, Y. J.; Miao, Q. Q.; Yi, X. Y.; Liang, G. L. Pyridine–biquinoline-metal complexes for sensing pyrophosphate and hydrogen sulfide in aqueous buffer and in cells. Analytical Chemistry 2015, 87(5), 2678-2684; [15] Sun, H. Y.; Lu, D. T.; Xian, M.; Dong, C.; Shuang, S. M. A lysozyme-stabilized silver nanocluster fluorescent probe for the detection of sulfide ions. Analytical Methods 2016, 8(22), 4328-4333.

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[16] Li, X.; Cheng, J.; Gong, Y. L.; Yang, B.; Hu, Y. Z. Mapping hydrogen sulfide in rats with a novel azo-based fluorescent probe. Bioprobes and Bioelectronics 2015, 65, 302-306. [17] Chen, W.; Pacheco, A.; Takano, Y.; Day, J. J.; Hanaoka, K.; Xian, M. A single fluorescent probe to visualize hydrogen sulfide and hydrogen polysulfides with different fluorescence signals. Angewandte Chemie International Edition 2016, 55, 9993-9996. [18] Chen, W.; Rosser, E. W.; Matsunaga, T.; Pacheco, A.; Akaike, T.; Xian, M. The development of fluorescent probes for visualizing intracellular hydrogen polysulfides. Angewandte Chemie International Edition 2015, 54, 13961-13965. [19] Ozdemir, T.; Sozmen, F.; Mamur, S.; Tekinay, T.; Akkaya, E. U. Fast responding and selective near-IR Bodipy dye for hydrogen sulfide sensing. Chemical Communications 2014, 50(41), 5455-5457. [20] Chan, Y. H.; Jin, Y. H.; Wu, C. F.; Chiu, D. T. Copper(II) and iron(II) ion sensing with semiconducting polymer dots. Chemical Communications 2011, 47(10), 2820-2822. [21] Wang, P.; Ma, X. Y.; Su, M. Q.; Hao, Q.; Lei, J. P.; Ju, H. X. Cathode photoelectrochemical sensing of copper(II) based on analyte-induced formation of exciton trapping. Chemical Communications 2012, 48(82), 10216-10218. [22] Prade, E.; Barucker, C.; Sarkar, R.; Ospelt, G. A.; Amo, J. M. L. d.; Hossain, S.; Zhong, Y. F.; Multhaup, G.; Reif, B. Sulindac sulfide induces the formation of large oligomeric aggregates of the Alzheimer's disease amyloid-β Ppeptide which exhibit reduced neurotoxicity. Biochemistry 2016, 1(5), 607-617. [23] Choi, S. J.; Jang, B. H.; Lee, S. J.; Min, B. K.; Rothschild, A.; Kim, I. D. Selective detection of acetone and hydrogen sulfide for the diagnosis of diabetes and halitosis using SnO2 nanofibers functionalized with reduced graphene oxide nanosheets. ACS Applied Materials & Interfaces 2014, 6(4), 2588-2597. [24] Lee, S.; Barin, G.; Ackerman, C. M.; Muchenditsi, A.; Xu, J.; Reimer, J. A.; Lutsenko, S.; Long, J. R.; Chang, C. J. Copper capture in a thioether-functionalized porous polymer applied to the detection of wilson’s disease. Journal of the American Chemical Society 2016, 138(24), 7603-7609. [25] Henthorn, H. A.; Pluth, M. D. Mechanistic insights into the H 2S-mediated reduction of aryl azides commonly used in H 2S detection. Journal of the American Chemical Society 2015, 137(48), 15330-15336. [26] Zhang, P. S.; Li, J.; Li, B. W.; Xu, J. S.; Zeng, F.; Lv, J.; Wu, S. Z. A logic gate-based fluorescent probe for detecting H 2S and NO in aqueous media and inside live cells. Chemical Communications 2015, 51, 4414-4416. [27] Lippert, A. R.; New, E. J.; Chang, C. J. Reaction-based fluorescent probes for selective imaging of hydrogen sulfide in living cells. Journal of the American Chemical Society 2011, 133(26), 10078-10080. [28] Lanza, A.; Germann, L. S.; Fisch, M.; Casati, N.; Macchi, P. Solid-state reversible nucleophilic addition in a Highly flexible MOF. Journal of the American Chemical Society 2015, 137(40), 13072-13078. [29] Beng, T. K.; Takeuchi, H.; Weberc, M.; Sarpong, R. ChemInform abstract: Stereocontrolled synthesis of vicinally functionalized piperidines by nucleophilic

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β-addition of alkyllithiums to α-Aryl substituted piperidine enecarbamates. Chemical Communications 2015, 51(36), 7653-7656. [30] Deng, J. C.; Kuo, C. W.; Chuang, S. C. Nucleophilic conjugate 1,3-addition of phosphines to oligoynoates. Chemical Communications 2014, 50(73), 10580-10583. [31] Chen, Y. C.; Zhu, C. C.; Yang, Z. H.; Chen, J. J.; He, Y. F.; Jiao, Y.; He, W. J.; Qiu, L.; Cen, J. J.; Guo, Z. J. A ratiometric fluorescent probe for rapid detection of hydrogen sulfide in mitochondria. Angewandte Chemie International Edition 2013, 52(6), 1688-1691. [32] Fu, Y.; Feng, Q. C.; Jiang, X. J.; Xu, H.; Li, M.; Zang, S. Q. New fluorescent probe for Cu(2+) and S(2-) in 100% aqueous solution based on displacement approach. Dalton Transactions 2014, 43(15), 5815-5822. [33] Sasakura, K.; Hanaoka, K.; Shibuya, N.; Mikami, Y.; Kimura, Y.; Komatsu, T.; Ueno, T.; Terai, T.; Kimura, H.; Nagano, T. Development of a highly selective fluorescence probe for hydrogen sulfide. Journal of the American Chemical Society 2011, 133(45), 18003-18005. [34] Zhang, L.; Lou, X.; Yu, Y.; Qin, J.; Li, Z. A new disubstituted polyacetylene bearing pyridine moieties: convenient synthesis and sensitive chemoprobe toward sulfide anion with high selectivity. Macromolecules 2011, 44(13), 5186-5193. [35] Strianese, M.; Pellecchia, C. Metal complexes as fluorescent probes for sensing biologically relevant gas molecules. Coordination Chemistry Reviews 2016, 318,16–28. [36] Galardon, E.; Tomas, A.; Roussel, P.; Artaud, I. New fluorescent zinc complexes: towards specific sensors for hydrogen sulfide in solution. Dalton Transactions, 2009, 42, 9126–9130. [37] Strianese, M.; De, M. F.; Pellecchia, C.; Ruggiero, G. Myoglobin as a new fluorescence probe to sense H2S. Protein & Peptide Letters, 2011, 18, 282–286. [38] Mirra, S.; Milione, S.; Strianese, M.; Pellecchia, C. A Copper Porphyrin for Sensing H2S in Aqueous Solution via a “Coordinative-Based” Approach. European Journal of Inorganic Chemistry, 2015, 13, 2272–2276. [39] Strianese M, Mirra S, Bertolasi V.; Milione, S.; Pellecchia, C.; Organometallic sulfur complexes: Reactivity of the hydrogen sulfide anion with cobaloximes. New Journal of Chemistry, 2015, 39, 4093–4099. [40] Wang, M. Q.; Li, K.; Hou, J. T.; Wu, M. Y.; Huang, Z.; Yu, X. Q. BINOL-based fluorescent probe for recognition of Cu(II) and sulfide anion in water. Journal of Organic Chemistry 2012, 77(18), 8350-8354. [41] Wang, Y.; Sun, H. H.; Hou, L. J.; Shang, Z. B., Dong, Z. M.; Jin, W. J. 1,4-Dihydroxyanthraquinone-Cu2+ ensemble probe for selective detection of sulfide anion in aqueous solution. Analytical Methods, 2013, 5(20), 5493-5500. [42] Liang, Z. H.; Tsoi, T. H.; Chan, C. F.; Dai, L. X.; Wu, Y. D.; Du, G. Y.; Zhu, L. Z.; Lee, C. S.; Wong, W. T.; Law, G. L.; Wong, K. L. A smart “off-on” gate for the in situ detection of hydrogen sulphide with Cu(II)-assisted europium emission. Chemical Science 2016, 7, 2151-2156. [43] Gao, C. J.; Liu, X.; Jin, X. J.; Wu, J.; Xie, Y. J.; Liu, W. S.; Yao, X. J.; Tang, Y. A retrievable and highly selective fluorescent probe for detecting copper and sulfide. Sensors & Actuators B Chemical 2013, 185(8), 125-131.

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[44] Chen, J.; Li, Y.; Lv, K.; Zhong, W. B.; Wang, H.; Wu, Z.; Yi, P. G.; Jiang, J. H. Cyclam-functionalized carbon dots probe for sensitive and selective detection of copper(II) ion and sulfide anion in aqueous media and its imaging in live cells. Sensors & Actuators B Chemical 2016, 224, 298-306. [45] Feng, X.; Zhang, T.; Liu, J. T.; Miao,J. Y.; Zhao, B. X. A new ratiometric fluorescent probe for rapid, sensitive and selective detection of endogenous hydrogen sulfide in mitochondria. Chemical Communications 2016, 52(15), 3131-3134. [46] Li, X.; Gong, Y. L.; Wu, K.; Liang, S. H.; Cao, J.; Yang, B.; Hua, Y. Z.; Han, Y. F. A highly sensitive and water soluble fluorescent probe for rapid detection of hydrogen sulfide in living cells. RSC Advances 2014, 4(68), 36106-36109. [47] Zhang, W.; Kang, J. Q.; Li, P.; Wang, H.; Tang, B. Dual signaling molecule probe for rapid detection of hydrogen sulfide based on modified tetraphenylethylene. Analytical Chemistry 2015, 87(17), 8964-8969. [48] Zhang, C. H.; Zhang, G. M.; Feng, L. H.; Li, J. F. A ratiometric fluorescent probe for sensitive and selective detection of hydrogen sulfide and its application for bioimaging. Sensors & Actuators B Chemical 2015, 216, 412-417. [49] Chen, J.; Li, Y.; Zhong, W. B.; Hou, Q. Y.; Wang, H.; Sun, X.; Yi, P. G. Novel fluorescent polymeric nanoparticles for highly selective recognition of copper ion and sulfide anion in water. Sensors & Actuators B Chemical 2015, 206, 230-238. [50] Zhu, Y. F.; Fan, A. H.; Shen, W. Z. A general chemical conversion route to synthesize various ZnO-based core/shell structures. Journal of Physical Chemistry C 2008, 112(28), 10402-10406. [51] Chen, J.; Zeng, F.; Wu, S. Z.; Su, J.; Zhao, J.; Tong, Z. A facile approach for cupric ion detection in aqueous media using polyethyleneimine/pmma core-shell fluorescent nanoparticles. Nanotechnology 2009, 20(36), 2844-2850.

ACCEPTED MANUSCRIPT One-pot fabrication of FRET-based fluorescent probe for detecting copper ion and sulfide anion in 100% aqueous media Kun Lv, Jian Chen*, Hong Wang, Peisheng Zhang*, Maolin Yu, Yunfei Long and

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Pinggui Yi

A FRET-based fluorescent probe PF for reversibly detecting copper ion and sulfide anion in water has been successfully developed by using a facile

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one-step method. The as-prepared fluorescent probe PF presented high selectivity, rapid time response, good reversibility and excellent long-term

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fluorescence stability (>50 days).

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A FRET-based fluorescent probe (PF) for reversibly detecting copper ion and sulfide anion has been developed. A facile one-step synthesis method. The probe (PF) shows good water dispersibility, rapid time response, good reversibility and excellent long-term fluorescence stability (>50 days).

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