Highly Selective Fluorescent Probe for the Sensitive Detection of

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A highly selective fluorescent probe for the sensitive detection of inorganic and organic mercury species assisted by H2O2 Wei Shu, Liangguo Yan, Jin Liu, Zuokai Wang, Shan Zhang, Chengcheng Tang, Caiyun Liu, Baocun Zhu, and Bin Du Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.5b02153 • Publication Date (Web): 07 Aug 2015 Downloaded from http://pubs.acs.org on August 13, 2015

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Industrial & Engineering Chemistry Research

A highly selective fluorescent probe for the sensitive detection of inorganic and organic mercury species assisted by H2O2 Wei Shu, Liangguo Yan,* Jin Liu, Zuokai Wang, Shan Zhang, Chengcheng Tang, Caiyun Liu, Baocun Zhu,* and Bin Du * School of Resources and Environment, University of Jinan, Shandong Provincial Engineering Technology Research Center for Ecological Carbon Sink and Capture Utilization, Jinan 250022, China *

Corresponding author. fax: +86-531-82767617; Tel.: +86-531-82767617

E-mail address: [email protected] (L. Yan), [email protected] (B. Zhu) and [email protected]

ACS Paragon Plus Environment


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Abstract Mercury (Hg) and its derivatives pose a serious threat to the environment and human health because of their durability, easy transference and high biological accumulation. Thus, the development of methods for selective and sensitive determination of Hg2+ is very important to understand its distribution and implement more

detailed

toxicological

studies.

Herein,

we

report

a

simple

4-hydroxynaphthalimide-derived fluorescent probe (1) for the detection of both inorganic and organic mercury species in aqueous solution. Probe 1 could quantificationally detect mercury species by fluorescence spectroscopy with high selectivity and sensitivity. Importantly, probe 1 could serve as a “naked-eye” indicator for mercury species and exhibited a large fluorescent enhancement with the help of hydrogen peroxide (H2O2). Additionally, the mechanism of the reaction between probe 1 and mercury species was confirmed using 1H-NMR and ESI-MS. And, analytical applications of probe 1 to the river water samples further demonstrated that it provided an excellent method for the determination of mercury species in the environment. Keywords: Fluorescent probe; naked-eye detection; Hg2+; methylmercury; 4-hydroxynaphthalimide; hydrogen peroxide


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1. Introduction Mercury (Hg) and its derivatives commonly found in the global environment pose a serious threat to the environment and human health because of their durability, easy transference and high biological accumulation.1-5 Organic forms of mercury coming from inorganic mercury ions (Hg2+), such as methylmercury species (CH3HgX, X = Cl-, Br-, AcO-, etc), is lipophilic, readily absorbed, and poorly excreted and can cause damage to the central nervous system and other organs.6-11 But, the ramifications of long-term and low-level exposure to methylmercury species are less clear and warrant thorough toxicological investigations.12-14 Thus, the development of methods for the determination of inorganic and organic mercury species is very important. Among the various reported methods for the determination of mercury species, fluorescent probes are widely developed due to their high sensitivity and operational simplicity.15-24 Despite advances in the development of fluorescent probes for Hg2+, few examples for the detection of organic mercury species have been reported.25-33 In addition, most of the reported fluorescent probes are based on polymers, foldamers, and biomolecules.34-36 While, some fluorescent probes still suffer from poor water-solubility and low sensitivity.37 Thus, novel water-soluble small molecular fluorescent probes with high selectivity and sensitivity for the simultaneous detection of inorganic and organic mercury species become our target. Herein,

we

describe

the

design

and

synthesis

of

a

simple

4-hydroxynaphthalimide-derived fluorescent probe (1) (Scheme 1) for the detection of both inorganic and organic mercury species in aqueous solution. In probe 1, we chose a dimethyl-thiocarbamic

ester

group

as

the

recognition

receptor

and

N-butyl-4-hydroxy-1,8-naphthalimide as the fluorophore because of its outstanding ICT structure and desirable photophysical properties.38-39 We hypothesize that the thioester



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group changes to ester moiety in the presence of mercury species, and the reaction of compound 3 with hydrogen peroxide results in the cleavage of a ester group, and as a result, restores the green fluorescence of N-butyl-4-hydroxy-1,8-naphthalimide. Although a similar reaction mechanism has been published by Churchill et al, millimolar concentrations Hg2+ and H2O2 were adopted to study its recognition properties and “AND” logic gate responses.38 Additionally, the recognition properties toward organic mercury species were not involved in the previous paper.38 However, in this paper, our proposed probe 1 could not only detect inorganic and organic mercury species quantitatively with high selectivity and sensitivity, but also serve as a “naked-eye” indicator for both mercury species with the help of H2O2. The reaction mechanism of probe 1 with mercury species assisted by hydrogen peroxide is shown in Scheme 2.

2. Experimental 2.1 Materials and general methods All the chemicals used in this paper were obtained from commercial suppliers and used without further purification. Ultrapure water was prepared through Sartorious Arium 611DI system and used throughout the experiment. Silica gel (200-300 mesh, Qingdao Haiyang Chemical Co.) was used for column chromatography. 1H NMR and 13

C NMR were recorded on a Bruker AV-400 spectrometer with chemical shifts reported

as ppm (in CDCl3, TMS as internal standard). Electrospray ionization (ESI) mass spectra were measured with an LC-MS 2010A (Shimadzu) instrument. Fluorescence emission spectra were carried out on a PerkineElmer Model LS-55 spectrophotometer with excitation wavelength of 450 nm. All the fluorescence spectra were uncorrected. All pH measurements were made with a Sartorius basic pH-meter PB-10. 2.2. Synthesis of N-butyl-4-hydroxy-1,8-naphthalimide


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N-butyl-4-chloro-1,8-naphthalimide

(856.5

mg,

2.7

mmol)

and

N-hydroxyphthalimide (489 mg, 3 mmol) were dissolved in 15 mL of dimethyl sulfoxide (DMSO). Then potassium carbonate (1.242 g, 9 mmol) was added and stirred at 80 °C for 6 h. After cooling to room temperature, ultrapure water (100 mL) was added to the reaction mixture, and the pH was adjusted to 3. The pure product was obtained by filtering reaction mixture (690 mg, 71%). The structure was confirmed to be N-butyl-4-hydroxy-1,8-naphthalimide.39 1H-NMR (400 MHz, DMSO-d6) δ (*10-6): 0.913(t, J = 7.2 Hz, 3H), 1.286-1.376(m, 2H), 1.546-1.619(m, 2H), 4.009(t, J = 7.2 Hz, 2H), 7.111(d, J = 8.0 Hz, 1H), 7.737(t, J = 7.8 Hz, 1H), 8.332(d, J = 8.0 Hz, 1H), 8.456 (d, J = 6.0 Hz, 1H), 8.524 (d, J = 8.4 Hz, 1H).

13

C-NMR (100 MHz, DMSO-d6) δ

(*10-6): 13.77, 19.88, 29.78, 110.07, 112.00, 121.72, 122.58, 125.34, 128.97, 129.26, 131.03, 133.61, 161.02, 162.97, 163.68. ESI-MS calcd for C16H16NO3 [M+H]+ 270.1130, found 270.1135. 2.3. Synthesis of Probe 1 To a solution of N-butyl-4-hydroxy-1,8-naphthalimide (534 mg, 2 mmol) and dimethylthiocarbamoyl chloride (494 mg, 4mmol ) in dry dichloromethane (10 mL) was added N-ethyldiisopropylamine (350 µL). The resulting mixture was stirred at room temperature until the reaction was complete. After evaporation of the solvent, the crude product was purified by silica column chromatography (CH2Cl2 as eluent) to get the pure probe 1 (163 mg, 23%).1H-NMR (400 MHz, DMSO-d6) δ (*10-6): 0.926(t, J = 7.6 Hz, 3H), 1.310-1.402(m, 2H), 1.579-1.654(m, 2H), 3.436(s, 3H), 3.509(s, 3H), 4.042(t, J = 7.4 Hz, 2H), 7.593(d, J = 8.4 Hz, 1H), 7.880(t, J = 7.8 Hz, 1H), 8.286(d, J = 8.4 Hz, 1H), 8.502-8.522(m, 2H).

13

C-NMR (100 MHz, DMSO-d6) δ

(*10-6): 13.73, 19.82, 29.64, 43.14, 119.79, 121.46, 122.39, 125.67, 127.57, 128.47,



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131.12, 131.16, 154.42, 162.78, 163.29, 185.39. ESI-MS calcd for C19H21N2O3S [M+H]+ 357.1273, found 357.1278. 3. Results and discussion The synthesis of probe 1 was given in Scheme 1. The structure of the target probe 1 was confirmed by 1H NMR,

13

C NMR, and MS. It is necessary to point out that the

synthetic method for N-butyl-4-hydroxy-1,8-naphthalimide fluorophore reported in this manuscript possesses many advantages including one-step synthesis, mild reaction conditions, simple workup, high yield. Obviously, the synthetic method is superior to other previous reports,40-42 and is anticipated it will be widely adopted to the synthesis of the important compound N-butyl-4-hydroxy-1,8-naphthalimide. 3.1. Characteristic spectra The spectral responses of probe 1 toward mercury species were investigated under aqueous solution containing 5 mM HEPES and 100 mM H2O2 at pH 7.4. In the absence of mercury species and H2O2, the probe solution exhibits one major absorption peak at 348 nm and a very weak fluorescence emission peak at 530 nm. The respective addition of Hg2+ or H2O2 to the probe solution, the absorption and fluorescence emission peak had no obvious changes. While Hg2+ and H2O2 were added to the solution of probe 1, the maximum absorption peak undergoes a red shift to 446 nm and the maximum emission peak at 552 nm exhibits a large enhancement (Fig. 1a and b). The absorption and fluorescence spectra of probe 1 after addition of Hg2+ and H2O2 are in good agreement with the corresponding spectra of N-butyl-4-hydroxy-1,8-naphthalimide.39 The results implied that both inorganic and organic mercury species could generate the cleavage of a ester group in the presence of H2O2 (Scheme 2). That is to say, our proposed probe could detect inorganic and organic mercury species. And, the color


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changes from colorless to yellow, showed probe 1 had the capability to detect mercury species by the naked-eye. 3.2. Assistant effect of H2O2 H2O2 was added to the reaction solution of probe 1 (5 µM) and Hg2+ (10 µM) in the aqueous solution containing HEPES (5 mM, pH 7.4). As shown in inset of Fig. 2, the continuous increases of fluorescence intensity were induced by the increasing concentrations of H2O2 (from 0 to 200 mM). The results implied that H2O2 could promote the cleavage of ester group, and amplified the response of probe 1 to mercury species.39 So, we chose 100 mM H2O2 as the amplification reagent in the detection of mercury species. On the other hand, our proposed probe could detect H2O2 in the presence of Hg2+. 3.3. Quantification of Hg2+ and CH3Hg+ Hg2+ was added gradually to the solution of 1 (5 µM) and H2O2 (100 mM). As shown in inset of Fig. 3a, the continuous enhancements of fluorescence intensity were induced by the increasing concentrations of Hg2+ (from 0 to 2 µM). Additionally, there was a good linearity between the fluorescence intensity and the concentrations of Hg2+ in the range of 0 to 2 µM with a detection limit of 2.4 nM (based on 3σ/k). The Environmental Protection Agency (EPA) has set a 2 ppb (10 nM) maximum tolerable level of mercury contamination in drinking water.18-19 Therefore, probe 1 can meet the requirement of detecting mercury species in drinking water. The similar phenomena were also observed in the presence of CH3Hg+ (Fig. 3b). There was a good linearity between the fluorescence intensity and the concentrations of CH3Hg+ in the range of 0 to 100 µM with a detection limit of 5.8 nM (based on 3σ/k). This allowed the determination of Hg2+ and CH3Hg+ by a turn-on fluorescence method with the high sensitivity (Table 1).



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3.4. Selectivity to Hg2+ For an excellent probe, high selectivity is a matter of necessity. The effects of common metal ions, such as K+, Na+, Zn2+, Ca2+, Ni2+, Cu2+, Ag+, Pb2+, Al3+, Fe3+, Fe2+, Mg2+, Cd2+, and cysteine, on fluorescence spectra of probe 1 were investigated. Compared with other metal ions, considerable change of the fluorescence intensity was observed for Hg2+ (Fig. 4a). Also, the effects of interference of common metal ions on monitoring Hg2+ were studied respectively (Fig. 4b). The results exhibited that our proposed probe 1 possesses excellent selectivity toward mercury species in the presence of other metal ions.25-33,45 In addition, we also evaluated the fluorescence behavior of probe 1 toward common anions species. The probe showed only little changes in the emission peak upon addition of various anions (F-, Cl-, Br-, I-, NO3-, NO2-, SO42-, SO32-, HSO3-, S2-, CO32-, HCO3-, and SCN-). Only Hg2+ induced a significant fluorescence enhancement (Fig. 4c). Moreover, this probe still exhibited a similar fluorescence profile for Hg2+ in the presence of the above-mentioned anions (Fig. 4d). These studies clearly indicated that the probe can be utilized for the selective detection of Hg2+ without interference from anions. The pH effects on the fluorescence spectra of probe 1 were examined. As shown in Fig. 4e, probe 1 is stable within a pH range from 4 to 10. Thus, probe 1 could detect mercury species without interference from pH of the environments. 3.5. Time-dependence of detecting Hg2+and CH3Hg+ The effect of reaction time on the fluorescence emission of the system was also studied and the results are shown in Fig. 5a and b. The fluorescence signal for the system increases rapidly with increasing reaction time under the above-mentioned analytical conditions, and then almost remains at reaction time greater than about 15


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min and 40 min for Hg2+ and CH3Hg+, respectively. Additionally, the pseudo-first-order rate constant was determined to be kobs = 0.4397 min-1 (for 10 µM Hg2+) and kobs = 0.0514 min-1 (for 10 µM CH3Hg+), respectively.44 Therefore, probe 1 would provide a fast analytical method for the determination of inorganic and organic mercury species.25-33,45 Additionally, the discrimination of Hg2+ and CH3Hg+ based on their different rates of desulfurization could be achieved. 3.6. Analytical application Three river water samples were collected from stream central line and near shore of the Yellow river at Jinan, China. Then, the water samples were filtered through filter paper and stored in the refrigerator. The amount of Hg2+ in the water samples was determined by our proposed method, and the results were not detected. Then 4 µM Hg2+ was added to above-mentioned samples. The results showed that the recoveries of Hg2+ in three river water samples containing 4 µM Hg2+ are 104.16-116.39% and the RSD is lower than 5.6%. These demonstrated that our proposed probe provided an excellent method for the determination of mercury species. 3.7. Mechanism of probe 1 in sensing mercury species In this analytical method, mercury species first made our proposed probe desulfurate

into

compound

3.

Then

compound

3

hydrolyzed

into

N-butyl-4-hydroxy-1,8-naphthalimide with the strong fluorescence. The obtained fluorescence

enhancement

was

due

to

the

production

of

N-butyl-4-hydroxy-1,8-naphthalimide. To further confirm the interaction mechanism of probe 1 with mercury species, the reaction of probe 1 with Hg2+ and CH3Hg+ was conducted singly under the same conditions as described above. The unique green fluorescent reaction product was



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obtained and characterized to be N-butyl-4-hydroxy-1,8-naphthalimide by 1H-NMR and ESI-MS.39 Therefore, a possible mechanism was proposed as shown in Scheme 2. 4. Conclusions In summary, we have presented the design, synthesis and properties of a 4-hydroxynaphthalimide-derived fluorescent probe 1 employed a dimethyl-thiocarbamic ester group as high selective recognition receptor for inorganic and organic mercury species. Probe 1 exhibited a high sensitivity toward mercury species with the help of hydrogen peroxide, and could detect quantitatively mercury species in real samples by turn-on fluorescence spectroscopy. Our proposed probe would open new opportunities to achieve the practical usage for the monitoring of environmentally inorganic and organic mercury species in aqueous solution. More importantly, we demonstrated that the dimethyl-thiocarbamic ester moiety is a new design strategy for the construction of highly selective and sensitive probes for the simultaneous of detection of inorganic and organic mercury species with the amplification reagent of H2O2. Acknowledgements We gratefully acknowledge financial support from the National Nature Science Foundation of China (No. 21107029, 21377046), Outstanding Young Scientists Award Fund of Shandong Province (BS2013HZ007), Postdoctoral Science Foundation of China (2013M541953). Associated content Supporting Information: This material is available free of charge via the Internet at http://pubs.acs.org. References (1) Jiang, G. B.; Shi, J. B.; Feng, X. B. Mercury pollution in China. Environ. Sci. Technol. 2006, 40, 3673.


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(39) Zhu, B.; Gao, C.; Zhao, Y.; Liu, C.; Li, Y.; Wei, Q.; Ma, Z.; Du, B.; Zhang, X. A 4-hydroxynaphthalimide-derived ratiometric fluorescent chemodosimeter for imaging palladium in living cells, Chem. Commun. 2011, 47, 8656. (40) Liu, T.; Xu, Z.; Spring, D. R.; Cui, J. A lysosome-targetable fluorescent probe for imaging hydrogen sulfide in living cells. Org. Lett. 2013, 15, 2310. (41) Ren, J.; Wu, Z.; Zhou, Y.; Li, Y.; Xu, Z. Colorimetric fluoride sensor based on 1,8-naphthalimide derivatives. Dyes Pigm. 2011, 91, 442. (42) Sun, W.; Li, W.; Li, J.; Zhang, J.; Du, L.; Li, M. Naphthalimide-based fluorescent off/on probes for the detection of thiols. Tetrahedron 2012, 68, 5363. (43) Zhu, B. C.; Wang, W. Z.; Liu, L. Y.; Jiang, H. L.; Du, B.; Wei, Q. A highly selective colorimetric and long-wavelength fluorescent probe for Hg2+. Sens. Actuators B: Chem. 2014, 191, 605. (44) Liu, C.; Wu, H.; Wang, Z.; Shao, C.; Zhu, B.; Zhang, X. A fast-response, highly sensitive and selective fluorescent probe for the ratiometric imaging of nitroxyl in living cells. Chem. Commun. 2014, 50, 6013. (45) Lee, M. H.; Lee, S. W.; Kim, S. H.; Kang, C.; Kim, J. S. Nanomolar Hg(II) detection using Nile blue chemodosimeter in biological media. Org. Lett. 2009, 11, 2101.



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Table caption and table Table 1. Comparison of fluorescent probes for Hg2+. Probe O N

LOD (nM)

Solution (v/v)

References

100

CH3CN–H2O (1:99)

[23]

800

CH3CN–H2O (1:1)

[24]

4.9

DMSO–H2O (5:95)

[25]

10

Ethanol–water (1:1)

[43]

2.4

Aqueous solution

This work

O

S HN S N

N S NH NH

NH

OH

O O

N

O

O HN

O O

NC CN

NC O O

O

N

O

O

S N


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Figure captions Fig. 1 (a) Fluorescence response of 1 (5 µM) toward Hg2+ (10 µM) and H2O2 (100 mM) in HEPES (5 mM, pH 7.4) aqueous solution. (b) Absorption response of 1 (15 µM) toward Hg2+ (30 µM) and H2O2 (100 mM) in HEPES (5 mM, pH 7.4) aqueous solution. Each spectrum was acquired 10 min after Hg2+ addition. Fig. 2. Fluorescence spectra of 1 (5 µM) in the presence of Hg2+ (10 µM) and increasing concentrations of H2O2 (final concentration: 0, 5, 10, 20, 50, 100, 200 µM) under HEPES (5 mM, pH 7.4) aqueous solution. Excitation wavelength = 450 nm. Each spectrum was acquired 10 min after Hg2+ addition. Fig. 3(a) Fluorescence spectra of 1 in the presence of increasing concentrations of Hg2+ (final concentration: 0, 0.05, 0.1, 0.4, 0.8, 1.4, 1.6, 2 µM). Each spectrum was acquired 10 min after Hg2+ addition. (b) Fluorescence spectra of 1 in the presence of increasing concentrations of CH3Hg+ (final concentration: 0, 5, 10, 20, 40, 60, 70, 80, 90, 100 µM). Excitation wavelength = 450 nm. Each spectrum was acquired 30 min after CH3Hg+ addition. Fig. 4. (a) Fluorescence responses of 1 (5 µM) toward Hg2+, Cu2+, Ag+ (10 µM) and other metal ions (50 µM) in H2O2 (100 mM), HEPES (5 mM, pH 7.4) aqueous solution. (b) Fluorescence responses of 1 (5 µM) toward Hg2+ (10 µM) in the presence of various metal ions with the help of H2O2 (100 mM) under HEPES (5 mM, pH 7.4) aqueous solution. (c) Fluorescence responses of 1 (5 µM) toward Hg2+ (10 µM) and anions (100 µM) in H2O2 (100 mM), HEPES (5 mM, pH 7.4) aqueous solution. (d) Fluorescence responses of 1 (5 µM) toward Hg2+ (10 µM) in the



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presence of various anions with the help of H2O2 (100 mM) under HEPES (5 mM, pH 7.4) aqueous solution. (e) Fluorescence intensity of 1 (5 µM) at 552 nm under different pH values. Excitation wavelength = 450 nm. Each spectrum was acquired 10 min after Hg2+ addition. Fig. 5. (a) Time-course of fluorescence intensity for 1 (5 µM) in the presence of Hg2+ (10 µM) and H2O2 (100 mM) at 552 nm. (b) Time-course of fluorescence intensity for 1 (5 µM) in the presence of CH3Hg+ (10 µM) and H2O2 (100 mM) at 552 nm.


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Figures

Fig. 1a.

Fig. 1b.



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Fig. 2.


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Fig. 3a.

Fig. 3b.



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Fig. 4a.

Fig. 4b.


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Fig. 4c.

Fig. 4d.

Fig. 4e.



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Fig. 5a.

Fig. 5b.


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Schemes and scheme captions Scheme 1 Synthesis of probe 1 Scheme 2 Reaction mechanism of 1 for mercury species with the help of H2O2

Scheme 1

Scheme 2



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TOC


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Highly Selective Fluorescent Probe for the Sensitive Detection of

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