Two high selective and sensitive ratiometric fluorescence probes for detecting hypochlorite

Accepted Manuscript Title: Two high selective and sensitive ratiometric fluorescence probes for detecting hypochlorite Author: Jiawei Li Caixia Yin Fangjun Huo Kangming Xiong Jianbin Chao Yongbin Zhang PII: DOI: Reference:

S0925-4005(16)30361-6 http://dx.doi.org/doi:10.1016/j.snb.2016.03.067 SNB 19872

To appear in:

Sensors and Actuators B

Received date: Revised date: Accepted date:

23-12-2015 14-3-2016 16-3-2016

Please cite this article as: Jiawei Li, Caixia Yin, Fangjun Huo, Kangming Xiong, Jianbin Chao, Yongbin Zhang, Two high selective and sensitive ratiometric fluorescence probes for detecting hypochlorite, Sensors and Actuators B: Chemical http://dx.doi.org/10.1016/j.snb.2016.03.067 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Two high selective and sensitive ratiometric fluorescence probes for detecting hypochlorite

Jiawei Li

a,1

, Caixia Yin a,*, Fangjun Huo b,**, Kangming Xiong a,1, Jianbin Chao b,

Yongbin Zhang

a

Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion

and Storage of Shanxi Province, Shanxi University, Taiyuan, 030006, China. b

Research Institute of Applied Chemistry, Shanxi University, Taiyuan, 030006, China.

*Corresponding

author:

C.X.

Yin,

E-mail:

[email protected],

Tel/Fax:

[email protected],

Tel/Fax:

+86-351-7011022. **Corresponding

author:

F.J.Huo,

E-mail:

+86-351-7018329.

1

Jiawei Li and Kangming Xiong contributed equally to this work

1

Graphical Abstract

Highlight  Two “turn-on” fluorescent probes, which are conveniently prepared were presented  Two probes showed high selective and sensitive recognition for ClO−  The mechanism was proved by 1H NMR and ESI-MS

2

Abstract:

In

this

work,

2-Naphthol

(1)

and

its

derivative

1-(2-hydroxynaphthalen-1-yl) naphthalen-2-ol (BINOL) (2) as two ratiometric fluorescence probes are used to detect hypochlorite, which is one of the biologically important reactive oxygen species (ROS), by UV–Vis and fluorescent spectrometers. The fluorescence intensity of probe 1 and 2 were gradually decreased when addition of ClO −. Also, the detailed signal mechanism was elucidated by 1H NMR and ESI-MS. In addition, the detection limits of probe 1 and 2 for ClO− were found to be 81 nM and 49 nM. Both two probes showed high selectivity for hypochlorite.

Keywords: Probes; Fluorescent; Ratiometric; Hypochlorite

3

1. Introduction The detection and quantification of inorganic anions have been invigorated over the past years from environmental, biological, and medical aspects. And a variety of probes that are able to selectively recognize anions were designed [1-6]. As a type of ROS, hypochlorous acid and its conjugate base hypochlorite (ClO−) are widely employed as strong oxidizing agents in our daily life. For example, Sodium hypochlorite is the most commonly used chlorinated substance and extensively used as a household cleaning agent and as disinfectant for treatments including drinking water, swimming pool water, treated wastewater for non-potable reuse and others [7-10]. In living organisms, hypochlorite is synthesized from hydrogen peroxide and chloride ions in a chemical reaction catalyzed by the enzyme myeloperoxidase (MPO) [11]. In the physiological pH solution, HOCl is partially dissociated into OCl−, and it plays a crucial role in vivo due to its antibacterial properties [12-13]. However, concentrated hypochlorite solutions have a potential health hazard to human and animals [14-15]. A large number of intake hypochlorite can lead to tissue damage and diseases such as hepatic ischemia-reperfusion injury [16], atherosclerosis [17], lung injury [18], rheumatoid [19-20], cardiovascular diseases [21], neuron degeneration [22], arthritis [23], and cancer [24-25]. Therefore, it is necessary to detect the hypochlorite (ClO−) content accurately and effectively. There are a number of methods available for the hypochlorite determination, such as the normalized and well-known iodometric titration, many colorimetric methods based on reaction of hypochlorite with organic reagents [26-32], chemiluminescence methods such as that based on fluorescein test strip [33-35], coulometric [36], polarographic, bromination of fluorescein [37], and radiolysis. However, fluorescent probe detection is a promising method for the detection of hypochlorous acid because of the high sensitivity and selectivity. As an organic synthetic raw material and dye intermediate, 2-Naphthol is widely used in our daily life. It is used in the spices, leather tanning agent, textile auxiliaries and so on. As the raw material, 1-(2-hydroxynaphthalen-1-yl) naphthalen-2-ol (BINOL) can be synthetized from it. Besides, BINOL has attracted particular interests 4

in asymmetric catalysis and fluorescent chemosensors due to their versatile backbone, which can be modified by strategic placement of functional groups based on steric and electronic properties [38-42]. In this work, two fluorescent probes (Scheme 1) have been reported as two ratiometric fluorescence probes for ClO−. The investigation shows that the changes of the probes on absorbance spectra and emission spectra after reaction with ClO− could be used for the detection of ClO−. 2. Experimental 2.1. Materials 4-(2-Hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) was purchased from Sigma-Aldrich (St. Louis, MO). All chemicals and solvents were of analytical grade without further purification. Deionized water was used to prepare all aqueous solutions. The solutions of anions were prepared from their sodium salts. 2.2. Instruments A pH meter (Mettler Toledo, Switzerland) was used to determine the pH. TLC analysis was performed using precoated silica plates. UV-vis absorption and fluorescence spectra were recorded on a Cary 50 Bio UV-Visible spectrophotometer and Cary Eclipse fluorescence spectrophotometer, respectively. Shanhai Huamei Experiment Instrument Plants, China provided a PO-120 quartz cuvette (10 mm). 1H NMR and 13C NMR experiments were performed with a Bruker AVANCE-300 MHz and 75 MHz NMR spec-trometer, respectively (Bruker, Billerica, MA). Coupling constants (J values) are reported in hertz. ESI determinations were carried out on an LTQ-MS (Thermo) instrument. 2.3. Preparation of Solutions of Probe 1 and Analytes. Stock solutions of probe 1 (20 mM) and 2 (20 mM) were prepared for measurements in acetonitrile (CH3CN) solution. Stock solutions (20 mM) of H2O2, ClO2−, F− , NO2−, S2−, SCN−, MnO4−, CO32− P2O74−, Br−, Cl−, SO42−, H2PO4−, HPO42−, HSO4−, HSO3− and ClO− were prepared by direct dissolution of proper amounts of 5

sodium salts in deionized water. Stock solution (1.34 mM) of Hypochlorous acid was prepared by dissolving sodium hypochlorite in deionized water. All chemicals used were of analytical grade. 2.4. General UV–vis and fluorescence spectra measurements All the detection experiments of probe 1 and 2 were measured in DMSO: H2O (v/v=1/1) and DMF solution, respectively. The fluorescence procedure were as follows: into DMSO: H2O (v/v=1/1) and DMF solution, containing 1.5 μM probe 1 and 50 μM probe 2, ClO− sample was gradually titrated, respectively. All fluorescence spectra data of probe 1 and 2 were recorded at 24 s and 6 s after ClO− addition.

3. Results and Discussion 3.1. The selectivity of probe for ClO− An important feature of probe is that it has special selectivity for a kind of analyte over other substance. To evaluate the hypochlorite-selective nature of probe, possible influences caused by other analytes were investigated for probe 1 and 2 respectively using the fluorescence spectra and UV–vis spectra. Fig. 1 and Fig. 2 showed that the fluorescence and absorbance changes that probe 1 and probe 2 undergone upon the addition of various oxidizing species, including H 2O2, ClO2− , F− , NO2−, S2−, SCN−, MnO4−, CO32− P2O74−, Br−, Cl−, SO42−, H2PO4−, HPO42−, HSO4−, HSO3− and ClO− in DMSO: H2O (v/v=1/1) and DMF respectively. The probe 1 (Fig. 1a) displayed a fluorescence enhancement (λex= 275 nm, slit: 5 nm/5 nm) in the presence of the ClO− (9.72 μM). Fig. 1b showed a visual fluorescence changes (colorless to blue) of probe 2 upon addition of ClO − (1.68 μM) in DMF. However, the other analytes induced no changes in fluorescence spectra and no changes in the UV-Vis spectra under the same conditions. In addition, we could see that the solution color of probe 1 before and after upon addition of ClO − changed from colorless to orange (Fig. 2a). We also noted that the probe 1 had strongly fluorescent enhancement under illumination with a 365 nm UV lamp. The probe 2 (50 μM) also displayed a fluorescence enhancement (λex= 385 nm, slit: 5 nm/5 nm) when added hypochlorite, while the other analytes 6

had no changes under illumination with a 365 nm UV lamp. The solution color of probe 2 before and after upon addition of ClO − changed from colorless to yellow (Fig. 2b). These signal changes indicated that probe 1 and 2 could serve as two selective chemosensors for hypochlorite. 3.2. UV–Vis and fluorescence spectra of detecting ClO− The UV-Vis absorption spectra of probe 1 and 2 with various ClO− concentrations was investigated and shown in Fig. 3. With increasing concentration of ClO− (0–10.72 μM), the absorption peaks of probe 1 (80 μM) at 252 nm and 290-300 nm were gradually increased, and a new band developed at 360 nm increased gradually. Four well-defined isosbestic points were noted at 268, 277, 312 and 334 nm, indicating a new compound generated and corresponding UV-vis spectra in Fig. 3a. Besides, Fig. 3b showed the changes in the UV-Visible spectrum upon addition of ClO− (0–0.47 μM) to a solution of the probe 2 (50 μM) in DMF. The absorption peak of probe 2 at 340 nm was gradually decreased and at 268-291 nm was gradually increased, then a new absorption peak appeared at 381 nm. Two well-defined isosbestic points appeared at 315, 345 nm. However, Fig.4a showed a regular changes in the fluorescence spectra upon addition of ClO− solution to a solution of the probe 1 (1.5 µM) in DMSO: H2O (v/v=1/1). The probe 1 was strongly fluorescent in the absence of ClO−. Upon increasing ClO− concentration, the initial fluorescence intensity of 360 nm gradually decreased and the fluorescence intensity of 434 nm gradually increased. A visual fluorescence change for the probe 1 was observed under illumination with a UV 365 nm lamp when the ClO− was added to the DMSO: H2O (v/v=1/1). Fig. 4b displayed the fluorescence response of the probe 2 (50 µM) to ClO− in DMF. The initial fluorescence intensity of 515 nm was gradually increased when added ClO−. All these indicated the formation of a new species. 3.3. Time-dependent and system-dependent for ClO− 7

More, time-dependent modulations in the fluorescence spectra of probe 1 (1.5 µM) and probe 2 (50 µM) were monitored in the presence of ClO− (Fig.S1, ESI†). The kinetic study showed that the reaction of probe 1 and probe 2 were completed within 24 s and 6 s for ClO−, respectively. It indicated that probes reacted rapidly with ClO− under the experimental conditions. These fast responses could provide the possibility of quantitative detection without any pretreatment of samples. We also investigated both probe 1 and 2 the system dependent for the determination of ClO− (Fig.S2, ESI†). Fig.S2 showed the fluorescence intensity obtained for the free probes and the probes-ClO− at different system solutions. It was obvious that the fluorescent signals of the probe 1 in the DMSO: H2O (v/v=1/1) and probe 2 in the DMF. There were no fluorescent enhancements or only partial changes for probe 1 and 2 in other systems when added ClO−. So the optimum system of probe 1 and 2 chose DMSO: H2O (v/v=1/1) and DMF. 3.4. Detection limits for ClO− To investigated the detection limits of two probes for ClO− (Fig. S3, ESI†), probe 1 and 2 was treated with various concentrations of ClO− and the fluorescence intensity at 360 nm and 515 nm were plotted as a function of ClO− concentration, respectively. The fluorescence intensity of probe 1 and 2 were linearly proportional to the ClO− concentrations, and the detection limits were 81 nM and 49 nM based on the definition by IUPAC (CDL= 3 Sb/m) [43]. Morever, the detection limits indicated that the two fluorescence probes showed a certain sensitivity towards ClO− that were comparable to the other synthetic probes for ClO− (Table.S1, ESI†) [44-49]. 3.5. Proposed detection mechanism The reaction mechanism of the present system was studied. We presumed that the color change and fluorescence enhancement could be attributed to the intermolecular dehydration reaction of phenolic hydroxyl groups. As we all known, the hydroxyl groups or phenolic hydroxyl groups can undertake intermolecular dehydration reaction in the presence of some of the catalysts. We speculate the mechanism is based on a specific reaction promoted by hypochlorite: namely probe 1 and probe 2 can undertake intermolecular dehydration reaction in the presence of hypochlorite. In 8

order to elucidate the detailed signal mechanism, ESI-MS analysis of reaction mixture of probes with ClO− was carried out (Fig.S4, ESI†). In addition, the binding pattern between probes and ClO− were also examined by the 1H NMR (Fig.S5, ESI†). Some signals of the probes disappeared: the phenolic hydroxyl groups of probe 1 and probe 2 at δ 9.690 and δ 5.030 were disappeared, respectively. These evidences clearly indicated that the mechanism what we speculated might be correct.

4. Conclusions In summary, we have developed two ratiometric fluorescence probes based on 2-Naphthol and its derivative BINOL for the detection of ClO− over other analytes. Both probe 1 and 2 had a high selectivity and sensitivity for ClO− over other analytes in DMSO: H2O (v/v=1/1) and DMF respectively. Morever, the detection limits of probe 1 and 2 for ClO− were found to be 81 nM and 49 nM. Thus, the probes are sensitive enough to monitor ClO− comparable to that of other reported ClO− chemosensors.

Acknowledgments The work was supported by the National Natural Science Foundation of China (No. 214 72118), the Shanxi Province Foundation for Returnee (No. 2012-007), the Taiyuan Technology star special (No. 12024703), the Program for the Top Young and Middle-aged Innovative Talents of Higher Learning Institutions of Shanxi (TYMIT, No. 2013802), and talents Support Program of Shanxi Province (No. 2014401).

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Ma,

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its

Biographies Jiawei Li She obtained her BSC in Chemistry for Shanxi University in 2014. Now she is studying for a master's degree in Institute of Molecular Science at Shanxi University. Her current research is molecular recognition chemistry. Caixia Yin She obtained her Doctor Degree in chemistry of Shanxi University in 2005. Now she is a Professor in Institute of Molecular Science of Shanxi University major in inorganic chemistry. Her current research interests are molecular recognition, sensors chemistry. Fangjun Huo He obtained his Doctor Degree in chemistry of Shanxi University in 2007. Now he is an Assoiate Professor in Research Institute of Applied Chemistry of Shanxi University major in organic chemistry. His current research interests are sensors, supramolecular chemistry. Kangming Xiong He obtained his BSC in Chemistry of Shanxi University in 2014. Now he is studying for a master's degree in Institute of Molecular Science at Shanxi University. His current research is molecular recognition chemistry. Jianbin Chao He obtained his master degree is in chemistry for Shanxi University in 2000. Now he is a Professor in Research Institure of Applied Chemistry at Shanxi University major in organic chemistry. His current research interests are supramolecular chemistry. Yongbin Zhang He obtained his master degree is in chemistry for Shanxi University in 2006. Now he is Assoiate Professor in Research Institute of Applied Chemistry of Shanxi University major in organic chemistry. His current research interests are molecular recognition, sensors chemistry.

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Figure captions Fig. 1 (a) The fluorescence intensity of probe 1 (1.5 μM) with ClO− (9.72 μM) and other various analytes (145 μM) in DMSO: H2O (v/v=1/1) (λex = 275 nm, slit: 5 nm/5 nm); (b) The fluorescence intensity of probe 2 (50 μM) with ClO− (1.68 μM) and other various analytes (2500 μM) in DMF (λex = 385 nm, slit: 5 nm/5 nm). Inset: two visual fluorescence color change photographs for ClO− and other analytes under illumination with a 365 nm UV lamp. Fig. 2 (a) The UV-Vis absorption spectra of probe 1 (8 μM) with ClO− (20.1 μM) and other various analytes (300 μM) in DMSO: H2O (v/v=1/1); (b) The UV-Vis absorption spectra of probe 2 (50 μM) with ClO− (0.47 μM) and other various analytes (1066 μM) in DMF. Inset: two color change photographs for ClO− and other analytes. Fig. 3 (a) Absorption spectra of the probe 1 (80 μM) in the presence of various concentrations of ClO− (0–10.72 μM) in DMSO: H2O (v/v=1/1); (b) The absorption spectra of the probe 2 (50 μM) in the presence of various concentrations of ClO− (0–0.47 μM) in DMF. Inset: two color change photographs for ClO−. Fig. 4 (a) Fluorescence spectra of probe 1 (1.5 μM) in the presence of various concentrations of ClO− (0–5.16 μM) in DMSO: H2O (v/v=1/1) (λex = 275 nm, slit: 5 nm/5 nm); (b) Fluorescence spectra of probe 2 (50 μM) in the presence of various concentrations of ClO− (0–1.68 μM) in DMF (λex =385 nm, slit: 5 nm/5 nm). Inset: two color change photographs for ClO−. Scheme 1. The structures of the probe 1 and 2.

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Figure 1(a)

(a) Figure 1(b)

(b)

18

Figure 2(a)

(a)

Figure 2(b)

(b)

19

Figure 3(a)

(a)

Figure 3(b)

(b)

20

Figure 4(a)

(a)

Figure 4(b)

(b)

21

Scheme 1

22