Detection of hydrogen sulfide by a novel quinolone-based “turn-on” chemosensor in aqueous solution

Accepted Manuscript Detection of hydrogen sulfide by a novel quinolone-based “turnon” chemosensor in aqueous solution

Seong Youl Lee, Hyo Jung Jang, Ji Hye Kang, Hye Mi Ahn, Cheal Kim PII: DOI: Reference:

S1387-7003(17)30602-0 doi: 10.1016/j.inoche.2017.09.004 INOCHE 6760

To appear in:

Inorganic Chemistry Communications

Received date: Revised date: Accepted date:

24 July 2017 29 August 2017 1 September 2017

Please cite this article as: Seong Youl Lee, Hyo Jung Jang, Ji Hye Kang, Hye Mi Ahn, Cheal Kim , Detection of hydrogen sulfide by a novel quinolone-based “turn-on” chemosensor in aqueous solution, Inorganic Chemistry Communications (2017), doi: 10.1016/j.inoche.2017.09.004

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Detection of hydrogen sulfide by a novel quinolone-based “turn-on” chemosensor in aqueous solution

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Seong Youl Lee, Hyo Jung Jang,* Ji Hye Kang, Hye Mi Ahn, Cheal Kim*

Department of Fine Chemistry and Department of Interdisciplinary Bio IT Materials, Seoul

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National University of Science and Technology, Seoul 139-743, Korea. Fax: +82-2-973-9149;

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Tel: +82-2-970-6693; E-mail: [email protected] and [email protected]

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Abstract

A novel quinolone-based fluorescent chemosensor 1 was designed and synthesized

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for hydrogen sulfide. Distinct “turn-on” fluorescence enhancement of 1 was observed upon the addition of S2- in aqueous solution. Sensor 1 showed high sensitivity toward S2- with the

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detection limit of 7.0 μM. The recognition properties of sensor 1 toward S2- were studied by using photophysical experiments and its reaction-based sensing mechanism was supported by

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ESI-mass spectroscopy analysis. Practically, the sensing ability of 1 for S2- was successfully

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applied in real water samples.

Keywords: hydrogen sulfide, quinoline, fluorescent, chemosensor

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Hydrogen sulfide is widely used in industrial activities, such as tanneries, dyes and cosmetic manufacturing, food processing plants and production of wood pulp [1]. As a result, hydrogen sulfide can be easily found in water as a by-product of the industrial processes [2]. Concentrations less than 1 mg/L give water a “musty” or “swampy” odor and concentration of 1–2 mg/L gives water the “disgusting” smell and makes it very corrosive to household plumbing [3]. Hydrogen sulfide is best known as a smell of rotten egg and has traditionally

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been considered as a toxic gas [4,5]. However, recent studies have demonstrated that this molecule has been recognized as the third gaseous transmitter with nitric oxide (NO) and

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carbon monoxide (CO) [6–8]. Hydrogen sulfide plays an important role in many biological

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processes, including relaxation of vascular smooth muscles, mediation of neurotransmission, inhibition of insulin signaling, and regulation of inflammation. Physiologically, the concentration of hydrogen sulfide ranges from nano- to milli-molar levels (10-100 µM in

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blood and may reach 600 µM in the brain of human) [9,10]. Once cells cannot regulate the concentration of hydrogen sulfide within the physiological range, it is related to diseases such

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as Alzheimer’s disease, Down’s syndrome and diabetes [11,12]. Therefore, the development of a novel chemosensor for the rapid and convenient detection of hydrogen sulfide is of great

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importance [13–17].

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Several different methods have been developed to date for detecting hydrogen sulfide, including high pressure liquid chromatography (HPLC), gas chromatography (GC), mass chromatography and electrochemical methods [18,19]. Although these methods are sensitive

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and accurate, an advanced instructor and complicated time-consuming sample pre-treatments are needed [20]. In contrast, fluorometric methods have been regarded as useful tools for

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sensing hydrogen sulfide due to their simplicity, rapidity, low costs and wide application. [21]. Various fluorescence probes for selective sensing of anions have been developed, such as quinoline, naphthalimide, anthracence, and quinone [22–29]. Besides them, the quinoline moiety is a well-known fluorophore and frequently adopted in designing a chemosensor owing to its distinct spectral properties and good photostability [30]. Triaminoguanidium chloride is used to synthesize the C3 symmetric molecule [31,32]. We envisioned that a chemosensor having quinoline and triaminoguanidium chloride moieties might effectively detect a certain analyte with fluorescence. Moreover, although C32

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symmetric molecule has often been used in the spectrophotometric determination for various ions, its application as a fluorometric chemosensor for hydrogen sulfide was not ever investigated [33]. Herein, we report a novel quinolone-based fluorescent chemosensor 1. Sensor 1 showed a highly selective fluorescence “turn-on” property upon binding to hydrogen sulfide.

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Moreover, 1 could be used to detect and quantify S2- levels in real water samples. The reaction-based sensing mechanism of S2- was explained by ESI-mass spectroscopy analysis.

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Chemosensor 1 was synthesized by the substitution reaction of triamoniguanidium chloride and 2-chloro-N-(quinolin-8-yl)acetamide with 81 % yield in buffer/acetonitrile

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mixture solution (Scheme 1) and characterized by 1H NMR, 13C NMR and elemental analysis. To examine the fluorescence sensing ability of 1 , the fluorescence spectral changes were

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studied in the presence of various anions (CN-, OAc-, F-, Cl-, Br-, I-, H2PO4-, BzO-, SCN-, N3-, NO3-, SO42- and S2-) in aqueous solution. When excited at 315 nm (Fig. 1), sensor 1 exhibited

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a weak fluorescence emission (λmax = 525 nm) with a low quantum yield (Φ = 0.00521), while the fluorescence intensity clearly increased in the presence of S2- (Φ = 0.01592). In contrast, no obvious fluorescent response behavior to other anions was observed under the

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identical conditions. These results suggested that sensor 1 can be used to sense hydrogen

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sulfide as a “turn-on” chemosensor. Importantly, it is the first example that chemosensor 1 with triaminoguanidium chloride moiety showed the fluorometric detection of S2-, to the best of our knowledge.

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To investigate the sensing properties of 1 toward S2-, fluorescence titration was conducted. Upon the addition of S2-, fluorescence intensity increased gradually and was

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saturated with 115 equiv of S2- (Fig. 2). Based on the fluorescence titration data, the binding constant for 1 with S2- was estimated to be 4.9 × 102 M-1 from Benesi-Hildebrand equation (Fig. S1) [34]. The detection limit (3σ/K) of sensor 1 as a fluorescence sensor for the analysis of S2- was found to be 7.0 µM (Fig. S2) [35]. The value is about three order lower than a Secondary Maximum Contaminant Level set (7.8 mM) for odor in drinking water as established by the EPA. The interaction between 1 and S2- was further examined through UVvis titration (Fig. 3). Upon gradual increase of S2- concentration, the bands at 267 nm and 388 nm gradually decreased while the absorption peak at 316 nm increased until it reached a 3

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limiting value (120 equiv). The presence of clearly defined isosbestic points at 280 nm and 355 nm implied that sensor 1 reacted with S2- to form a stable species. To determine the stoichiometric ratio of 1 and S2-, Job plot analysis [36] was carried out using emission titration experiments in the presence of various molar fractions of S2- (Fig. S3). A maximum emission was observed when the molar fraction reached 0.5, suggesting that

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the formation between 1 and S2- has a stoichiometric ratio of 1:1. In order to understand the sensing mechanism, ESI-mass spectrometry analysis of 1 with Na2S was performed (Fig. 4). A peak at m/z = 281.00 was corresponded to the formation of [2-hydrazinyl-N-(quinolin-8-

[2,2'-(methylenebis(hydrazine-2,1-diyl))bis(N-(quinolin-8-yl)acetamide)thiol

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to

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yl)acetamide + H+ + 2CH3OH]+ (calcd. m/z = 281.16), and that at m/z = 533.00 was assigned +

Na+]+

(calcd. m/z = 553.12). These results suggested that the electron-poor triaminoguanidium

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moiety of 1 underwent the nucleophilic substitution by S2-. Based on Job plot and ESI-mass analysis, we proposed the sensing mechanism of 1 with hydrogen sulfide in Scheme 2.

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One of the important criterions for a selective sensor is the ability to detect a specific ion in the presence of other competing ions. The emission (at 525 nm) of 1-S2- species remained unperturbed in the presence of different anions such as CN-, OAc-, F-, Cl-, Br-, I-,

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H2PO4-, BzO-, SCN-, N3-, NO3- and SO42-) (Fig. 5). These results suggested that 1 can be used

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as an excellent selective sensor for S2- detection in the presence of the competing anions. The influence of pH on the detection properties of 1 for S2- was examined in bufferCH3OH (9:1, v/v) solution at various pH values ranging from 2 to 12 (Fig. 6). A stable and

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strong fluorescence intensity of 1-S2- species was observed between pH 7 and 9. This result S2-.

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warranted its application under environmental conditions, without any change in detection of

For practical application, we constructed a calibration curve for the determination of 2-

S by 1 (Fig. S4). A good linear relationship was observed for 1-S2- species with a correlation coefficient of R2 = 0.9929 (n = 3). To evaluate the practical abilities of 1 with S2-, drinking water, tap water and simulated wastewater [37] samples were selected and analyzed with three replicates. As shown in Table 1, satisfactory recoveries and suitable R.S.D. values for S2- were obtained. These results suggested that chemosensor 1 could be useful for the 4

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measurements of S2- in chemical and environmental applications. In conclusion, we reported a novel quinolone-based fluorescence chemosensor 1, which displayed highly selective and sensitive fluorescence enhancement toward S2- in aqueous solution. The detection limit (7.0 μM) of 1 for S2- was about three order lower than a Secondary Maximum Contaminant Level set (7.8 mM) for odor in drinking water as established by the EPA. The “turn-on” fluorescence of 1, based on the nucleophilic

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substitution by S2-, was supported by ESI-mass spectrometry analysis. Importantly, it is the first example that chemosensor 1 with triaminoguanidium chloride moiety showed the

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fluorometric detection of S2-, to the best of our knowledge. For practical application, 1 could

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be used to detect and quantify S2- levels in real water samples. Therefore, this work shows

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promise for the design and application of new hydrogen sulfide chemosensors.

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Acknowledgements

Basic Science Research Program through the National Research Foundation of Korea (NRF) funded

by

the

Ministry

of

Education,

Science

and

Technology

(NRF-

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2014R1A2A1A11051794) are gratefully acknowledged. This work was also supported by

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Korea Environment Industry & Technology Institute (KEITI) through "The Chemical Accident Prevention Technology Development Project", funded by Korea Ministry of

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Environment (MOE) (No. 2016001970001).

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Scheme 1. Synthesis of 1.

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Scheme 2. Proposed sensing mechanism of hydrogen sulfide by1.

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Table 1. Determination of S2- in water samples a S2- added (µmol/L)

S2- found (µmol/L)

Drinking water

0.0

0.0

300

293.2

0.0

0.0

300 0.0

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500

R.S.D. (n=3) (%)

97.7

13.5

297.1

99.0

8.1

101.9

11.4.

0.0 509.6

Conditions: [1] = 20 μmol L-1 in 10 mM bis-tris buffer-CH3OH solution (9:1, pH 7.0). b 239

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a

Recovery (%)

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Simulated wastewaterb

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Tap water

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Sample

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µmol/L of Na+, 281 µmol/L of K+, 288 µmol/L of Mg2+, 25 µmol/L of Ca2+, 160 µmol/L of F-, 98.7 µmol/L of Cl-, 10.5 µmol/L of PO43-, 20.8 µmol/L of SO42-, 48.4 µmol/L of NO3-, 12.3 µmol/L of HCO3- and 500 µmol/L of S2- were artificially added into 1 in bis-tris buffer-CH3OH

solution (9:1, pH 7.0).

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Figure captions Fig. 1 Fluorescence spectral changes of 1 (20 μM) in the presence of 115 equiv of different anions in a mixture of buffer and CH3OH (9:1, v/v). Fig. 2 Fluorescence spectral changes of 1 (20 μM) in the presence of different concentrations of S2- in a mixture of buffer and CH3OH (9:1, v/v) at room temperature. Inset: Plot of the

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fluorescence intensity at 530 nm as a function of S2- concentration.

Fig. 3 Absorption spectral changes of 1 (20 μM) in the presence of different concentrations of

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S2- in a mixture of buffer and CH3OH (9:1, v/v) at room temperature.

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Fig. 4 Positive-ion electrospray ionization mass spectrum of 1 upon addition of 1 equiv of S2-.

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Fig. 5 Competitive selectivity of 1 (20 μM) toward S2- (115 equiv) in the presence of other anions (115 equiv).

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Fig. 6 Fluorescence intensities (526 nm) of 1 (20 M) and 1-S2- species, respectively, at pH

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2-12 in a mixture of buffer and CH3OH (9:1, v/v) at room temperature.

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1+S2-

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250

1, 1+CN-, OAc-, F-, Cl-, Br-, I-, H2PO4-, BzO-,

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N3-, SCN-, NO3-, SO42-

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Fluorescence Intensity

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0 450

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Wavelength (nm)

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Fig. 1

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Fig. 2

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Fig. 3

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Fig. 4

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Fig. 5

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Fig. 6

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Graphical abstract

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Highlights

 A fluorescence “turn-on” chemosensor 1 for hydrogen sulfide was developed.

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 Sensor 1 showed the high sensitivity toward S2- with the detection limit of 7.0 μM.

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 Sensor 1 could be used to quantify S2- in real water samples.

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 The “turn-on” fluorescence mechanism of 1, based on the nucleophilic substitution by S2-, was explained by ESI-mass analysis.

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