Reactive Fluorescent and Colorimetric Probe for Highly Selective and Sensitive Detection of Hg 2+ in Real Water Samples

doi:10.21203/rs.3.rs-4868320/v1

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Reactive Fluorescent and Colorimetric Probe for Highly Selective and Sensitive Detection of Hg 2+ in Real Water Samples

https://doi.org/10.21203/rs.3.rs-4868320/v1

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Construction of efficient chemosensors for highly specific and sensitive detection of mercury ions remains a great challege. In this work a highly selective and sensitive probe CY was designed and synthesized by using coumarin fluorophore as the matrix and thioacetal moiety as the reactive recognition site for Hg²⁺. By virtue of the thiophilicity of Hg²⁺, probe CL could be hydrolyzed to deprotect and the thioacetal was tansformed to the acyl group after the addition of Hg²⁺, the blue-green fluorescence was quenched and meanwhile the solution changed from light green to yellow. The detection limit of probe CY for Hg²⁺ was as low as 6.8 nM, and it could completely react with Hg²⁺ within 3 min. Moreover, probe CY exhibited good resistance against interference from competitive metal ions and biothiols, high stability in pH 1–12 and applicability for fluorogenic and chromogenic dual-modal detection of Hg²⁺ in real water samples over a broad range of pH 5–10.

Coumarin

Fluorescent probe

Mercury(II)

Colorimetric

Thioacetal

With the development of modern industry, the extensive use of heavy metal ions especially Hg²⁺ ions has posed a serious threat to the environment and human life due to their significant biological accumulation and high toxicity [1, 2]. Elemental mercury can exist in the air for up to two years and is very easy to diffuse [3]. Therefore, the problem related to the deposition of mercury in the environment should not be underestimated, and Hg²⁺ will accumulate in the human body through the biological chain effect [4]. After ingesting food contaminated with Hg²⁺, Hg²⁺ is easily absorbed by the gastrointestinal tract and enters the body's circulatory system, thus, the transport of mercury ions to the target organs is promoted and biological poisoning is caused, resulting in severe damage to the nervous system, endocrine system, respiratory system, kidney, lung function, etc [5 − 7], causing serious damage to human health. Therefore, it is particularly important to find a method that can efficiently detect Hg²⁺. There are many methods that can detect Hg²⁺. Common methods include atomic fluorescence spectrometry [8], atomic absorption spectrometry [9], electrochemistry and other methods [10], but they are not widely used due to their high cost and complex detection instruments. However, fluorescent chemical sensors are used as an important means to detect mercury ions due to their advantages of cheap and easy availability, high sensitivity and rapid detection [11 − 15]. The fluorescent probes can recognize Hg²⁺ mainly through Hg²⁺-induced reactions and complexation between Hg²⁺ and ligands [16 − 21]. The reactions promoted by thiophilic Hg²⁺ ions mainly include deprotection reaction of thioacetals or thioketals [22 − 32], desulfurization reaction of thioesters [33 − 36], desulfurization cyclization reaction [37 − 39], desulfurization transformation of thiocarbonyl compounds to the corresponding carbonyl compounds [40, 41], and desulfurization elimination [42]. Though enormous fluorogenic chemosensors for Hg²⁺ sensing have been fabricated from various platforms, highly efficient fluorescent probes that are structurally simple and can be readily synthesized for selective, sensitive, and rapid detection of Hg²⁺ ions in real water samples over a broad pH range are rare and are urgently needed. We designed a new fluorescent probe CY by using coumarin fluorophore as the matrix and introducing thioacetal moiety as the reactive recognizing site for Hg²⁺ by virtue of the thiophilic property of Hg²⁺, as showed in Scheme 1. Before addition of Hg²⁺, CY showed strong blue-green fluorescence in EtOH/H₂O (1:1, v/v). After addition of Hg²⁺, hydrolytic deprotection of thioacetal was promoted, the blue-green fluorescence was quenched, and the solution changed from light green to yellow. The detection of Hg²⁺ features high selectivity, high sensitivity with the detection limit being as low as 6.8 nM, and rapid response within 3 min. Moreover, probe CY showed high stability and could be utilized for detection of Hg²⁺ in pH range of 5 − 10, thus had good application potential in the detection of Hg²⁺ in real water samples.

Reagents and Instruments

Unless otherwise noted, all reagents and solvents used in this study are analytically pure and purchased from commercial sources and used upon receipt. The melting point was determined by using WRS-2A capillary melter and the resulting temperature was not corrected. Nuclear magnetic resonance (NMR) spectroscopy was measured by Bruker AM-400 spectrometer. Thermo-QE plus was used for high resolution mass spectrometry. UV-Vis absorption spectra were determined by Shimadzu UV-1800 ultraviolet-visible and near-infrared spectrophotometer. Fluorescence emission spectra were determined by Hitachi FS5 fluorescence spectrophotometer.

Synthesis of Probe CY

To a flask containing dichloromethane (30 mL), compound 1 (0.917 g, 3 mmol) and 1,2-ethyldimercaptan (0.25 mL, 3 mmol) was added boron trifluoride ether solution (0.5 mL, 3.99 mmol) dropwise at 0 ℃ and under nitrogen atmosphere. The mixture was stirred under an ice bath for 4 h. After reaction the crude product was obtained by evaporation. The target probe CY was obtained as yellow solid (0.85 g, 74%) by recrystallization from ethanol, m.p. 170 − 171°C. IR (KBr pellet): ν 2972, 2927, 1701, 1618, 1587, 1510 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ 1.22 (t, 6H, J = 7.1 Hz, CH₃), 3.24 − 3.37 (m, 2H, CH₂), 3.35 − 3.48 (m, 6H, CH₂), 5.71 (d, 1H, J = 9.6 Hz), 6.49 (d, 1H, J = 2.9 Hz), 6.61 (dd, 1H, J = 8.9, 2.5 Hz), 7.27 − 7.36 (m, 2H), 8.01 (s, 1H). ¹³C NMR (101 MHz, CDCl₃): δ 12.47, 33.43, 44.99, 71.78, 83.44, 96.60, 108.20, 109.38, 114.83, 128.26, 129.81, 130.07, 141.79, 151.31, 155.84, 159.11. HR-MS: m/z 382.0690 (M + H)+; calcd. for C₁₈H₂₀ClNO₂S₂ 381.0624.

Measurement of Absorption and Fluorescence Spectra

Probe CY was dissolved in N,N-dimethylformamide (DMF) to prepare a stock solution (20 µM) for spectral measurement. Before fluorescence and UV-Vis absorption spectral tests, cysteine (Cys), L-homocysteine (Hcy), glutathione (GSH), LiNO₃, NaNO₃, KNO₃, AgNO₃, Cu(NO₃)₂·3H₂O, FeSO₄·7H₂O, Zn(NO₃)₂·6H₂O, Co(NO₃)₂·6H₂O, NiCl₂·6H₂O, Mn(NO₃)₂·4H₂O, SrCl₂·6H₂O, Hg(OAc)₂, CaCl₂, MgCl₂, Al(NO₃)₃·9H₂O, CrCl₃·6H₂O, Fe(NO₃)₃·9H₂O were dissolved in deionized water. For the fluorescence spectrum test, the excitation wavelength in ethanol system is 410 nm, and the excitation and emission slits are both 10.0 nm.

Synthesis of the Target Probe CY

Synthesis of the target probe CL was accomplished as showed in Scheme 2. Compound 1 was synthesized by using Vilsmeier-Haack reaction according to literature procedure [43]. Probe CY was formed by protecting the formyl group in compound 1 through the condensation reaction with 1,2-ethyldimercaptan catalyzed by BF₃·Et₂O, and the yield was 74%. The chemical structure of probe CL was confirmed by ¹H NMR (Fig. S1), ¹³C NMR (Fig. S2), FT-IR (Fig. S3), and high-resolution mass spectrum (HR-MS, Fig. S4). The spectral data were consistent with the structure of probe CL.

Fluorescence Emission Spectra of CY in Different Solvents

Fluorescence emission spectra of probe CY (20 µM) were tested in different solvents including ethanol (EtOH), acetonitrile (MeCN), DMF and dimethyl sulfoxide (DMSO), as showed in Fig. 1. It was observed that probe CY exhibited two emission peaks at 450 nm and 540 nm, respectively. When different solvents were used, the corresponding wavelengths of the two peaks did not change much, and the fluorescence intensity was slightly different. It could be seen that CY displayed the maximum fluorescence intensity in ethanol. Therefore, we used ethanol as the solvent for the follow-up test.

Fluorescence Spectra of Probe CY in EtOH/H₂O with Different Water Content

In order to explore the applicability of probe CL in the environment closer to realistic conditions, we tested the fluorescence emission spectra of probe CY in EtOH/H₂O with different water content from 10–90% (Fig. S5). The fluorescence intensity change at 530 nm within 30 min was monitored to determine the performance of the probe. When the water content increased from 10–50%, the fluorescence intensity of CY at 530 nm did not change significantly. When the water content was 60%, it was found that the fluorescence intensity of CY at 530 nm decreased slightly and a slight blue shift occurred for the fluorescence emission wavelength. The emission peak of CY in EtOH/H₂O with 70–90% water content shifted from 530 nm to about 500 nm. Moreover, the fluorescence intensity decreased with the increase of water content. Based on these results, a water content of 50%, namely, EtOH/H₂O (1:1, v/v) was selected for testing.

Specific Recognition of Hg²⁺ by Probe CY

Changes in the color of probe CY (20 µM) in EtOH/H₂O (1:1, v/v) after adding 5 eqivalents of different metal ions (Li⁺, Na⁺, K⁺, Ag⁺, Cu²⁺, Fe²⁺, Hg²⁺, Zn²⁺, Co²⁺, Ni²⁺, Mn²⁺, Sr²⁺, Ca²⁺, Mg²⁺, Al³⁺, Cr³⁺, Fe³⁺) or biothiols (Cys, Hcy, GSH) were recorded as showed in Fig. 2a. Addition of Hg²⁺ caused distinct color change from light green to yellow, while other metal ions and biothiols did not bring about noticeable color change. Under the irradiation of 365 nm UV light, probe CY solution emitted blue-green fluorescence which was quenched upon addition of Hg²⁺. UV-Vis absorption spectra of probe CY (20 µM) in EtOH/H₂O (1:1, v/v) before and after addition of different metal ions or biothiols were showed in Fig. 2b, which revealed that the absorption peak of probe CY shifted from 425 nm to 474 nm after Hg²⁺ was added. Changes in the fluorescence emission spectra of probe CY (20 µM) in EtOH/H₂O (1:1, v/v) after adding different metal ions and biothiols (Li⁺, Na⁺, K⁺, Ag⁺, Cu²⁺, Fe²⁺, Hg²⁺, Zn²⁺, Co²⁺, Ni²⁺, Mn²⁺, Sr²⁺, Ca²⁺, Mg²⁺, Al³⁺, Cr³⁺, Fe³⁺, Cys, Hcy, GSH) were showed in Fig. 2c. After the addition of Hg²⁺ the fluorescence intensity at 482 nm reduced sharply and the fluorescence was almost quenched due to the hydrolytic deprotection of thioacetal induced by Hg²⁺. No significant change was observed after the addition of other competitive ions, indicating that probe CY had good selectivity to Hg²⁺. Therefore, CY can be used as a fluorescent chemosensor for the detection of Hg²⁺ and can realize the naked eye recognition of Hg²⁺.

Anti-Interference Test of Probe CY to Detect Hg²⁺

In order to further verify whether probe CY is highly selective to Hg²⁺ in the presence of common competitive metal ions and biothiols, fluorescence emission spectra of probe CY (20 µM) with 5 eqivalents of different metal ions and biothiols were tested in EtOH/H₂O (1:1, v/v). Changes in fluorescence intensity at 482 nm of probe CY (20 µM) in EtOH/H₂O (1:1, v/v) after addition of 5 eqivalents of different competitive ions and biothiols and additional 5 eqivalents of Hg²⁺ were showed in Fig. 3. Obviously, the addition of different competitive metal ions and amino acids to the solution containing probe CY and Hg²⁺ did not cause significant changes in fluorescence intensity at 482 nm. The results demonstrated that probe CY had good anti-interference ability and could be utilized for highly selective detection of Hg²⁺ in the presence of excessive competitive metal ions and biothiols.

Detection Limit of Probe CY to Identify Hg²⁺

In order to test the detection limit of probe CY, fluorescence titration experiments were carried out. Fluorescence emission spectra of probe CY (20 µM) in EtOH/H₂O (1:1, v/v) after adding different concentrations of Hg²⁺ were measured and the changes in fluorescence intensity at 482 nm with the concentration of Hg²⁺ were plotted (Fig. S6). The results showed that the fluorescence intensity of probe CY first significantly decreased and then tended to be flat with the increase of Hg²⁺ concentration. The fluorescence intensity exhibited a good linear relationship with Hg²⁺ concentration (20–60 µM). The linear fitting equation was Y = − 494550.6X + 3.1 × 10⁷ with R² = 0.9706. The detection limit of probe CL for Hg²⁺ ions was calculated to be 6.8 nM according to the formula L = 3S/K, where L denotes the detection limit, S represents the standard deviation of fluorescence intensity of blank, and K is slope of the calibration curve. The results revealed the high sensitivity of probe CL for detection of Hg²⁺.

Response Time of Probe CY to Hg²⁺ and Effect of pH

Considering response time is an important factor affecting probe sensitivity, we studied the response time of probe CY to Hg²⁺ by measuring the changes in fluorescence intensity at 482 nm of probe CY (20 µM) in EtOH/H₂O (1:1, v/v) with time after addition of 5 equivalents of Hg²⁺, as showed in Fig. 4a. Probe CY could react with Hg²⁺ completely within 180 seconds, achieving a transient quenching effect, indicating that probe CY had a high sensitivity for the detection of Hg²⁺. At the same time, the influence of different pH environments on the recognition of Hg²⁺ by probe CY was also investigated. Fluorescence intensities at 482 nm of probe CY (20 µM) in EtOH/H₂O (1:1, v/v) under different pH values (1–13) were determined and showed in Fig. 4b. Probe CY could exist stably in the range of pH value 1–12 and the specific recognition of Hg²⁺ could be achieved in the range of pH 5–10.

Possible Sensing Mechanism

Plausible sensing mechanism of probe CY for detection of Hg²⁺ was proposed as showed in Scheme 3. It was concluded that the thioacetal moiety of probe CY was hydrolyzed to form an acyl group after adding Hg²⁺ due to the thiophilic nature of Hg²⁺ [22 − 32]. To further prove this deprotection mechanism, HR-MS of probe CY after addition of Hg²⁺ was obtained (Fig. S7). The spectrum clearly indicated that the molecular ion peak of probe CY located at m/z 382.0690 (Fig. S4) disappeared and the quasi-molecular ion peak at m/z 306.0884 corresponding to compound 1 (M⁺ + H, calcd. for C₁₆H₁₇ClNO₃ 306.0897) was visible after Hg²⁺ was added. This provided definitely evidence for the deprotection of the thioacetal moiety in probe CY to form compound 1 in the presence of Hg²⁺.

Detection of Hg²⁺ in Real Water Samples

The potential of probe CY in detecting Hg²⁺ in tap water and Jingyue Lake water was demonstrated. To the samples containing probe CY were added different concentrations of Hg²⁺ in tap water and Jingyue Lake water. Changes in color and fluorescence emission of probe CY (20 µM) in EtOH/H₂O (1:1, v/v) after addition of different concentrations of Hg²⁺ in tap water and Jingyue Lake water under natural light and 365 nm UV lamp were showed in Fig. 5. Bright green fluorescence was observed for the sample obtained from probe CL in the tap water under the 365 nm UV lamp. After adding different concentrations (40–100 µM) of Hg²⁺, the color of the solution gradually changed from light green to yellow, while the blue-green fluorescence gradually darkened, till the fluorescence quenching occurred. Similar changes were observed when different concentrations of Hg²⁺ were added to samples prepared from probe CL in Jingyue Lake water, indicating that probe CY had the potential to detect Hg²⁺ in real water samples by the fluorescent and colorimetric dual-mode.

Performance Comparison of Probe CL with Other Fluorescent Probes for Detection of Hg²⁺

To compare the sensing performance of probe CL with other reported fluorescent probes for detection of Hg²⁺, several related parameters including sensing medium, limit of detection (LOD), response time, and applicable pH range were listed in Table 1. It could be found that very few probes exhibited LOD lower than 10 nM. Probe 1 displayed a low LOD of 1.34 nM and a wide applicable pH range of 2.0–9.0, but its response time was 15 min thus could not qualify for rapid detection of Hg²⁺ [26]. Probe Ag/r-GO@RhB showed a low LOD of 2 nM in water, yet it could not be used in alkaline conditions [44]. Aa a comparison, probe CL featured the following advantages: (1) Highly specific for Hg²⁺ detection, immune from the interference of competitive metal ions and biothiols; (2) Highly sensitive to Hg²⁺, with a low LOD of 6.8 nM and a short response time of 3 min; (3) Stable in environments of pH 1–12 and applicable for fluorogenic and chromogenic dual-modal Hg²⁺ detection in real water samples over a broad range of pH 5–10.

Table 1

Performance comparison of probe CL with other fluorescent probes for detection of Hg²⁺
Probe	Medium	LOD for Hg²⁺	Response time	Applicable pH range	Reference
K1	H₂O	0.16 µM	0.5 min	7–11	[16]
L3	DMSO/H₂O (9:1)	14.94 nM	–	2.0–9.0	[17]
L1	EtOH	3.96 µM	–	3–11	[19]
DW	HEPES	6.53 nM	–	7–10	[21]
CY1OH2S	HEPES	0.32 µM	5 min	5–10	[24]
probe 1	CH₃CN/buffer (1:3)	1.34 nM	15 min	2.0–9.0	[26]
TPEH	EtOH/HEPES (2:8)	81.7 nM	< 100 s	6–8	[28]
AIE-COOH	DMSO/PBS (5:95)	22 nM	~ 100 s	5.8–7.8	[29]
TzAr-Nap-Hg	DMF/HEPES (1:3)	0.253 µM	80 min	7.4	[34]
DCM-Hg	DMSO/PBS (1:1)	3.35 µM	30 min	7–9	[36]
Coa-SH	DMF/PBS (1:9)	0.63 µM	10 min	7–12	[42]
Ag/r-GO@RhB	H₂O	2 nM	7 min	4–7	[44]
IQ	CH₃CN/H₂O (1:99)	0.86 µM	–	7–8	[45]
Nibt	H₂O	8.7 nM	30 s	4.0–11.0	[46]
yCQDs	PBS	45.0 nM	–	6.0–8.0	[47]
CY	EtOH/H₂O (1:1)	6.8 nM	3 min	5–10	this work

By introducing thioacetal structure into coumarin matrix, a reactive fluorescent and colorimetric probe CY was designed and synthesized, which could be used for efficient detection of Hg²⁺. After addition of Hg²⁺ to probe CL (20 µM) in EtOH/H₂O (1:1, v/v), the blue-green fluorescence was quenched, and the solution changed from light green to yellow. The recognition mechanism was verified by HR-MS to be based the Hg²⁺-promoted deprotection of thioacetal. The probe showed multiple advantages. The synthetic procedure is simple, the detection limit is as low as 6.8 nM, and the response time is 3 min. Moreover, Hg²⁺ can be detected in the pH range of 5–10 and the probe has a good application prospect in real water samples. The approach may provide helpful choices for the development of dual-modal fluorescent and colorimetric probes for highly slective and sensitive detection of Hg²⁺ in environmental samples.

Author Contribution

J. Y., Y. S. and H. L. wrote the main manuscript text; J. Y. and K. Z. performed research and analyzed the data. Y. Z. and Y. W. prepared the figures. All authors reviewed the manuscript.

o Availability of data and materials: Yes, our manuscript has data included as electronic supplementary material.

o Competing interests: 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.

o Funding: The Funding for the Open Research Program of State Key Laboratory of Molecular Engineering of Polymers, Fudan University (K2022-38 to Yanxi Song) is acknowledged.

o Authors' contributions (all authors should be included): Jiarui Yang, Yanxi Song and Hongqi Li wrote the main manuscript text; Jiarui Yang and Kaiqiang Zhang performed research and analyzed the data. Yong Zhao and Yihan Wu prepared the figures. All authors reviewed the manuscript.

o Code availability (software application or custom code): Not applicable.

o Ethics Approval: Not applicable.

o Consent to Participate: Not applicable.

o Consent to Publication: Not applicable.

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Scheme 1 to 3 are available in the Supplementary Files section.

No competing interests reported.

Supplementarymaterial.doc
schem1.png
Scheme 1 Features of the designed fluorescent probe CY for Hg²⁺ detection
scheme2.png
Scheme 2 Synthetic route to probe CY
scheme3.png
Scheme 3 Possible sensing mechanism of probe CY toward Hg²⁺

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You are reading this latest preprint version

Reactive Fluorescent and Colorimetric Probe for Highly Selective and Sensitive Detection of Hg 2+ in Real Water Samples

Status:

Version 1

Abstract

Figures

Introduction

Experimental

Reagents and Instruments

Synthesis of Probe CY

Measurement of Absorption and Fluorescence Spectra

Results and Discussion

Synthesis of the Target Probe CY

Fluorescence Emission Spectra of CY in Different Solvents

Fluorescence Spectra of Probe CY in EtOH/H₂O with Different Water Content

Specific Recognition of Hg²⁺ by Probe CY

Anti-Interference Test of Probe CY to Detect Hg²⁺

Detection Limit of Probe CY to Identify Hg²⁺

Response Time of Probe CY to Hg²⁺ and Effect of pH

Possible Sensing Mechanism

Detection of Hg²⁺ in Real Water Samples

Performance Comparison of Probe CL with Other Fluorescent Probes for Detection of Hg²⁺

Conclusions

Declarations

Author Contribution

References

Scheme

Additional Declarations

Supplementary Files

Status:

Version 1

Reactive Fluorescent and Colorimetric Probe for Highly Selective and Sensitive Detection of Hg 2+ in Real Water Samples

Status:

Version 1

Abstract

Figures

Introduction

Experimental

Reagents and Instruments

Synthesis of Probe CY

Measurement of Absorption and Fluorescence Spectra

Results and Discussion

Synthesis of the Target Probe CY

Fluorescence Emission Spectra of CY in Different Solvents

Fluorescence Spectra of Probe CY in EtOH/H2O with Different Water Content

Specific Recognition of Hg2+ by Probe CY

Anti-Interference Test of Probe CY to Detect Hg2+

Detection Limit of Probe CY to Identify Hg2+

Response Time of Probe CY to Hg2+ and Effect of pH

Possible Sensing Mechanism

Detection of Hg2+ in Real Water Samples

Performance Comparison of Probe CL with Other Fluorescent Probes for Detection of Hg2+

Conclusions

Declarations

Author Contribution

References

Scheme

Additional Declarations

Supplementary Files

Status:

Version 1

Fluorescence Spectra of Probe CY in EtOH/H₂O with Different Water Content

Specific Recognition of Hg²⁺ by Probe CY

Anti-Interference Test of Probe CY to Detect Hg²⁺

Detection Limit of Probe CY to Identify Hg²⁺

Response Time of Probe CY to Hg²⁺ and Effect of pH

Detection of Hg²⁺ in Real Water Samples

Performance Comparison of Probe CL with Other Fluorescent Probes for Detection of Hg²⁺