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Aug 14, 2017 - 99 3dr South Ring Road, Changshu, Jiangsu. 215500, China. •S Supporting Information. ABSTRACT: Nanocatalysts depended colorimetric ...
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Sensitive Colorimetric Assay of H2S Depending on the High-Efficient Inhibition of Catalytic Performance of Ru Nanoparticles Yuan Zhao,† Yaodong Luo,† Yingyue Zhu,‡ Yali Sun,† Linyan Cui,† and Qijun Song*,† †

Key Lab of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu 214122, China ‡ School of Biotechnology and Food Engineering, Changshu Institute of Technology, No. 99 3dr South Ring Road, Changshu, Jiangsu 215500, China S Supporting Information *

ABSTRACT: Nanocatalysts depended colorimetric assay possesses the advantage of fast detection and provides a novel avenue for the detection of hydrogen sulfide (H2S). The exploration of nanocatalysts with superior catalytic activity is challenging to achieve ultrasensitive colorimetric assay of H2S. Herein, 1.7 ± 0.2 nm ruthenium nanoparticles (Ru NPs) were prepared and exhibited outstanding catalytic hydrogenation activity. The degradation rate constants of orange I in the presence of Ru NPs were 4-, 47- and 165-fold higher than those of platinum (Pt) NPs, iridium (Ir) NPs and control groups without catalysts. H2S-induced deactivation of Ru NP catalysts was designed for the sensitive colorimetric assay of H2S, attributing to the poor thiotolerance of Ru NPs. A standard linear curve between the rate constants and the concentration of H2S was established. The limit of detection (LOD) was as low as 0.6 nM. A Ru NPs based colorimetric principle was also used to fabricate colorimetric paper strips for the on-site visual analysis of H2S. The proposed approach shows potential prospective for the preparation of highly selective colorimetric NP sensors for specific purposes. KEYWORDS: Ru nanoparticles, Catalytic activity, H2S detection, Colorimetric assay, Paper strips

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INTRODUCTION

based colorimetric methods have been widely exploited for the detection of H2S (Table 1). Nanocatalysts depended colorimetric assay, by contrast, possesses the advantages of simple operation, fast responses and high sensitivity, and is convenient to achieve on-site visual analysis of H2S. However, the conventional and reported catalysts are mainly limited to Au NPs, Ag NPs, Au@Pt NPs and graphene, etc.3,6,14−16 The detection sensitivity of colorimetric assay is still far from satisfying, and its performance is still restricted due to the limited catalytic property of the used NPs. With the rapid development of nanocatalysts, Ru NPs as a transition metal show superior catalytic hydrogenation activities, and have been investigated and employed in the reduction of nitroaromatic compounds and azo dyes.17 Nevertheless, studies on Ru NPs are limited to the exploration of novel synthetic methods and the investigation of shapedetermined catalytic properties,18−22 but Ru NP catalysts as a signal amplifier for the colorimetric assay are not explored. The mechanism of H2S induced Ru NP catalysts deactivation is not fully understood, and it is imperative and challenging to evaluate the deactivation degrees using Ru NPs-triggered catalytic system.

H2S along with nitric oxide and carbon monoxide are wellknown environmental pollutants and the endogenous gasotransmitter.1,2 H2S as one of the most important exhaled gaseous signaling molecules plays a significant role in a variety of physiological and pathological processes.3 Its level is not only an important environmental index but also is linked to various diseases (e.g., Alzheimer’s disease, Down’s syndrome, diabetes and liver cirrhosis).4−6 It is necessary to propose a powerful monitoring sensor for the precise investigation of H2S. Currently, the most common analysis for H2S detection mainly focuses on the instrumental analysis (such as gas chromatography, gas chromatography−mass spectrometry), fluorescence methods and colorimetric sensors, etc.1,5,7,8 However, instrumental analysis often requires tedious sample preparation or sophisticated equipment, and is not suitable for routine laboratory and on-site analyses.1,9 Fluorescence methods mainly depend on the fluorescence of probes, which are easily interrupted by the quenching effects due to the oxygen, humidity and foreign species.5,10 Alternatively, colorimetric assay gains increasing attention, attributing to the simple detection by naked eyes, short assay time, relatively low cost and no requirements for skillful technicians.3 Due to the unique fluorescence properties, localized surface plasmon resonance and catalytic performances of NPs,2,5,6,11−13 NPs © 2017 American Chemical Society

Received: May 8, 2017 Revised: July 15, 2017 Published: August 14, 2017 7912

DOI: 10.1021/acssuschemeng.7b01448 ACS Sustainable Chem. Eng. 2017, 5, 7912−7919

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ACS Sustainable Chemistry & Engineering

NPs and Ir NPs at the same concentration were compared by measuring the degradation kinetic curves at 512 nm in the reduction of orange I. Colorimetric Sensor for the Detection of H2S. Na2S generally exists in the form of HS− under alkaline condition, and is widely used as the source of H2S in solution.2,4,11,24 An amount of 20 μL different concentrated stock solution of Na2S (0, 5, 10, 20, 40, 60, 80, 100, 200, 400, 600 and 800 nM) was mixed with 10 μL of Ru NPs, respectively. The Na2S−Ru NPs solution was added into the mixtures of 4 μL of 10 mM orange I and 2 mL of 0.8 M N2H4. UV−vis absorption spectrum of orange I was measured at 512 nm by monitoring the degradation kinetic curves in the presence of different concentration of Na2S donors. Specificity and Reproducibility. The specificity of the developed method was explored for the detection of other sulfhydryl compounds, such as Cys and GSH. An amount of 20 μL of 2 μM Na2S donors and amino acids (His, Als, Thr, Arg, Asp, Glu, Tyr, Phe, Cys and GSH) were added to the mixture of Ru NPs, orange I and N2H4, respectively. The degradation kinetic curves of orange I were monitored. The selectivity of the proposed colorimetric assay was assessed in the presence of other interfering substances, including NaCO3, NaHCO3, NaNO2, NaNO3, NH4Cl, NaSO4, Na2S2O8 and NaSO3. An amount of 20 μL of 200 nM Na2S donors and 20 μL of 2 μM different interfering substances were added to the mixtures of Ru NPs, orange I and N2H4, respectively. The mixtures were applied to evaluate the selectivity in the monitoring of H2S. The reproducibility of the developed colorimetric sensor was investigated for the detection of H2S in Tai lake water. An aliquot of 1 mL of negative Tai lake water was filtrated three times to remove other substances. An amount of Na2S donors was spiked into the mentioned 1 mL of negative Tai lake water with the final concentration of 30, 50, 70, 90, 300 and 500 nM. The concentration of Na2S was measured by the developed colorimetric sensors at the same detection procedures. Fabrication of Paper Strip for H2S Gas Detection. A paper strip was fabricated for the visual detection of H2S gas. Generally, an aliquot of 10 μL of 1 M NaOH solution was added into 1 mL of 4 mM orange I, and the color of orange I was red under alkaline conditions. Filter papers (1 cm × 1 cm) were soaked with the above solution. After 1 min, filter papers were got out, and then 5 μL of Ru NPs was injected onto the filter papers. The prepared filter papers were dried at 40 °C oven for 10 min, and then were placed in a clear glass container (500 mL in volume). H2S gas is prepared by a stoichiometric reaction between Na2S and diluted H2SO4. An amount of 0.5 mmol Na2S was added into a sealed flask (500 mL), and then 0.4 mL of H2SO4 (0.1 mmol) was slowly injected. Different amounts of H2S gas were obtained by a micro syringe and separately injected into the above container with the prepared filter papers. The final concentration of H2S gas was 0, 1, 10 and 100 μM. After incubatiion for 5 min, an aliquot of 5 μL of 0.8 M N2H4 solution was added onto the surface of orange I−Ru NPs modified filter papers. The color changes of filter papers were recorded at 2 min for visual detection of H2S gas. The fabricated paper strips were also applied to study the effect of the interference gases using their dissolved forms, involving CO32−, HCO3−, NO2−, NO3−, NH4+, SO42−, S2O82−, SO32−. To explore the efficacy of colorimetric paper strips, the concentration was designed to 2 μM for interfering substances and 200 nM for Na2S. Instrumentation and Measurements. The UV−vis spectra were recorded in the range of 200−900 nm using a double beam UV−vis spectrophotometer with a 1 cm quartz cuvette (Model TU-1901). XPS analysis was performed on a PHI5000 Versa Probe high-performance electron spectrometer (Japan), using monochromatic Al Kα radiation (1486.6 eV), operating at accelerating voltage of 15 kV. Phase identification of the Ru NPs were conducted with X-ray diffraction (XRD, D8, Bruker AXS Co., Ltd.) using Cu Kα radiation source (λ = 1.54051 Å) over the 2θ range of 3−90°. High-resolution transmission electron microscopy (HRTEM, JEM-2100, Japan Electron Optics Laboratory Co., Ltd.) was performed at 200 kV to characterize the structure of NPs. The ζ-potential of Ru NPs was surveyed by using ζ-

Table 1. Comparison of LODs of NPs Based Colorimetric Sensors for H2S Detection Signals Luminescence

NPs

Fluorescence

Upconversion NPs Carbon nanodots Au nanoclusters

UV−vis absorption UV−vis absorption

Au NPs Ag NPs

UV−vis absorption UV−vis absorption Localized resonance scattering Catalytic properties

Ag NPs Au nanorods Au@Ag NPs

Catalytic properties

Au@Pt NPs

Catalytic properties Catalytic properties

Au NPs Ru NPs

Fluorescence

Graphene

Linear range

LODs

refs

0−100 μM

/

4

5−100 μM

0.7 μM

37

7−100 μM

0.73 μM 2.4 μM 0.35 μM 0.2 μM 0.2 μM 50 nM

7

3−45 μM 0.8−6.4 μM 0.7−10 μM 0.5−5 μM 0.05−100 μM 40−400 μM 10−100 nM 0.5−10 μM 5−100 nM

3 38 11 36 5

25.3 μM 7.5 nM

6

80 nM 0.6 nM

15 this work

14

In this paper, uniform Ru NPs were synthesized and showed superior catalytic hydrogenation activities for the degradation of orange I. Orange I−Ru NPs as an amplifier system was first designed for the sensitive and selective colorimetric monitoring of H2S, depending on H2S-induced poisoning of the catalytic active sites of Ru NPs. The degradation kinetic curves of orange I−Ru NPs amplifier were investigated in the presence of different concentrations of H2S, and the color fading process of orange I was monitored. The relationship between H2S concentration and the degradation rate constants of orange I was established, and the LOD was as low as 0.6 nM. The proposed Ru NPs based colorimetric assay can be served as an innovative signal transduction and amplification method for the sensitive detection of H2S.

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EXPERIMENTAL SECTION

Materials and Reagents. Ruthenium chloride hydrate (RuCl3· nH2O) was purchased from J&K Chemical CO., Ltd. Poly(vinylpyrrolidone) (PVP), ethylene glycol, hydrazine hydrate (N2H4, 85%), orange I, anhydrous acetone, histidine (His), alanine (Als), threonine (Thr), arginine (Arg), aspartic acid (Asp), glutamic acid (Glu), tyrosine (Tyr), phenylalanine (Phe), cysteine (Cys) and glutathione (GSH), NaCO3, NaHCO3, NaNO2, NaNO3, NH4Cl, NaSO4, NaSO3, Na2S2O8 and Na2S were all purchased from Sinopharm Chemical Reagent Co., Ltd. All reagents were of analytical-reagent grade and were used without further purification. Synthesis of Ru NPs. 12.3 mg of RuCl3 and 55.5 mg of PVP were dissolved in 10 mL of ethylene glycol at room temperature. The mixture was heated at 170 °C for 6 h. The color of the solution changed from dark red to dark brown and finally to dark brown. An aliquot of 10 mL Ru NPs solution was purified by anhydrous acetone for three times and then dispersed to 625 μL of ultrapure water. The concentration of Ru NPs was calculated to be about 1.6 μM according to the previous reported procedures.14 PVP stabilized Pt NPs and Ir NPs were respectively prepared according to the previous methods.17,23 The average sizes of Pt NPs and Ir NPs were 3.8 ± 1.3 nm and 1.9 ± 0.5 nm (Figure S1, Supporting Information). Catalytic Hydrogenation Performance of Ru NPs. An aliquot of 4 μL 10 mM orange I was mixed with 2 mL of 0.8 M N2H4 solution. And then, an amount of 10 μL Ru NPs, Pt NPs, Ir NPs was added into the above solution, respectively. The final concentration of Ru NPs in the system was about 8 nM. The catalytic performances of Ru NPs, Pt 7913

DOI: 10.1021/acssuschemeng.7b01448 ACS Sustainable Chem. Eng. 2017, 5, 7912−7919

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ACS Sustainable Chemistry & Engineering potential/nanometer particle size analytical instrument (Brookhaven Instruments Corporation).

analyzed from about 85 Ru NPs (Figure 1b). Representative HR-TEM images revealed that the lattice fringes of Ru NPs were separated by 0.236 nm. Ru NPs exhibited hexagonalclosepacked (hcp) crystal structures, which was in accordance with the XRD patterns (Figure 1c,d).17,18 The oxidation state of Ru NPs was characterized by XPS spectra (Figure 2a,b). Two peaks at 280.2 and 285.3 eV were attributed to the binding energies of 3d5/2 for Ru NPs in the zero oxidation state, and the binding energy at 281.1 and 287.1 eV was assigned to the high valence state of RuO2 3d5/2, owing to surface oxidized of Ru(0) during the XPS sampling procedure (Figure 2a).25,26 C 1s exhibited a peak located at 284.8 eV in the XPS spectra. Figure 2b shows two peaks at 462.0 and 463.5 eV, corresponding to the binding energies of Ru(0) 3p3/2 and RuO2 3p3/2, respectively.25−27 Additionally, when Ru3+ was reduced to Ru0, the absorption peak at 308 nm for Ru3+ generally decreased and finally disappeared, and the color of the solution changed from dark red to dark brown, indicating the formation of Ru NPs (Figure 2c). The ζpotential of Ru NPs solution was measured to be −22.0 mV (Figure 2d), indicating the excellent stability of Ru NPs.23 The hydroxyl from PVP endowed Ru NPs with negatively charge, which further stabilized them against agglomeration by electrostatic repulsion. Catalytic Hydrogenation Performances of Ru NPs. Orange I as an azo dye could be quickly degraded to aromatic amines in the presence of Ru NPs and N2H4, ascribing to the breakage of the −NN− bonds (Figure S1, Supporting Information).17 The catalytic performances of Ru NPs in the reduction of orange I were compared with Pt NPs, Ir NPs and the control group without catalysts. Under alkaline conditions, the color of orange I was red with the maximum absorbance of 512 nm (Figure S2, Supporting Information). The changes in the absorption at 512 nm as a function of time were monitored in the presence of different catalysts. As demonstrated in Figure 3a, the absorption at 512 nm showed no obvious changes for the control groups and Ir NPs within 2.0 min, and the degradation process generally took around 12 h. However, the absorption at 512 nm exhibited a sharp decline under the catalysis of Ru NPs. Even though orange I could also be degraded using Pt NPs as catalysts, the degradation kinetics curve was much slower than that of Ru NPs (Figure S3, Supporting Information). The degradation rate constants of orange I for Ru NPs were 4-, 47- and 165-fold higher than that of Pt NPs, Ir NPs and control groups (Figure 3a). The superior catalytic hydrogenation performances of Ru NPs can be ascribed to the vacant orbitals and the strong coordination effect with N2H4. Ru NPs acted as an electron mediator transferred the electron and hydrogen from N2H4 to azo bonds, leading to the degradation and decolorization of orange I.17,28 Meanwhile, the catalytic degradation reaction could also be inhibited after the addition of H2S, due to H2Striggered catalytic poisoning and the deactivation efficiency of Ru NP catalysts.3,29,30 Therefore, the degradation kinetics curve became slower after the addition of H2S, and the color of orange I did not change to colorless but became lighter when Ru NPs and H2S both existed (Figure 3b). Ru NPs Based Colorimetric Assay of H2S. The catalytic hydrogenation reaction of orange I using Ru NPs as catalysts could be applied to detect H2S. The logarithm plot of the absorbance at 512 nm with reaction time in the presence of different concentrations of Na2S donors was investigated. As demonstrated in Figure 4a, with the increasing concentration of

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RESULTS AND DISCUSSION Ru NPs Based Colorimetric Principle for H2S Assay. A schematic diagram illustrated the mechanism of the proposed Ru NPs based colorimetric assay of H2S (Scheme 1). Ru NPs Scheme 1. Schematic Illustration of Colorimetric Assay of H2S Depending on the Catalytic Hydrogenation Activity of Ru NPs

exhibited superior catalytic hydrogenation performance in the degradation of azo dyes. Ru NPs were applied to attack the azo bonds of orange I, leading to the rapidly degradation of orange I to aromatic amines or hydrazine derivatives through the hydrogenation reduction (Scheme 1a). Red colored orange I could be rapidly degraded to colorless using Ru NPs as catalysis and N2H4 as reducing agents. When H2S existed, the poor thiotolerance of Ru NPs induced the poisoning of the catalytic active sites of Ru NPs and deactivated the catalytic performances of Ru NPs. With the increasing concentration of H2S, the degradation kinetic curves of orange I became slow and the degradation rate constants decreased (Scheme 1b). There was a linear relationship between the concentration of H2S and the degradation rate constants. The color of orange I gradually faded under the H2S triggered Ru NPs catalytic system, and a paper strip sensor was fabricated for successful detection of H2S using the optimized sensor solutions. Preparation and Characterization of Ru NPs. Ru NPs stabilized by PVP were synthesized by the reduction of RuCl3 in the presence of ethylene glycol at 170 °C for 6 h. As illustrated in TEM images (Figure 1a), Ru NPs showed good monodispersity and uniform morphology. The average diameter of Ru NPs was 1.7 ± 0.2 nm, which was statistically 7914

DOI: 10.1021/acssuschemeng.7b01448 ACS Sustainable Chem. Eng. 2017, 5, 7912−7919

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Figure 1. (a) TEM images of synthesized Ru NPs. (b) Statistic analysis of the size of Ru NPs. (c) Respective HR-TEM images of Ru NPs. (d) XRD patterns of Ru NPs.

Figure 2. (a,b) XPS spectra of Ru NPs. (c) UV−vis spectra of RuCl3 and Ru NPs. Inset: photograph of Ru NPs solution. (d) ζ-potential of Ru NPs.

800 nM (R2 = 0.9981) (Figure 4c,d). The LOD was calculated to be 0.6 nM based on 3σ criterion (Supporting Information), which was much sensitive than those of previous reported approaches (Table 1). The sensitivity for the specific H2S detection was determined by the superior catalytic activity of Ru NPs and H2S-triggered catalytic deactivation efficiency of Ru NPs. The single Ru NPs

Na2S donors, the degradation kinetics curve of orange I became slower, and the color of orange I became deepened. As illustrated in Figure 4b, the kinetic rate constants decreased with the increasing concentration of Na2S donors.31 The standard linear curves between rate constants and the concentration of Na2S donors was established with a good correlation in the range of 5−100 nM (R2 = 0.9923) and 200− 7915

DOI: 10.1021/acssuschemeng.7b01448 ACS Sustainable Chem. Eng. 2017, 5, 7912−7919

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Figure 3. (a) Time-dependent absorbance of orange I at 512 nm in the presence of Ru NPs, Pt NPs and Ir NPs. (b) Time-dependent absorbance of orange I at 512 nm under the catalysis of Ru NPs before and after the addition of H2S. Inset: corresponding photographs of orange I at different conditions.

Figure 4. (a) Time-dependent absorbance of orange I at 512 nm in the presence of Ru NPs and different concentration of Na2S donors. Inset: photographs of orange I within 2 min after the addition of Ru NPs and different concentration of Na2S. (b) Linear fit plots of ln(A0/At) vs time at different concentration of Na2S. (c) Rate constants as a function of Na2S concentration ranging from 5 to 100 nM. (d) The rate constants as a function of Na2S concentration ranging from 200 to 800 nM.

absorption at 512 nm under the same concentration of GSH, Cys and H2S was due to the spatial effect and steric hindrance from various molecules. H2S molecules were easy to expose HS−, and thus could directly contact Ru NP catalysts to deactivate the catalytic active sites on the surface. Selectivity Evaluation. The developed colorimetric assay was planned to achieve ultrasensitive detection of H2S in the atmosphere, and thus the existing biological thiols in biologicalsystem could not interfere the detection results. The selectivity of the developed colorimetric assay was further assessed by challenging the system with interfering gases using their dissolved forms, involving CO32−, HCO3−, NO2−, NO3−, NH4+, SO42−, S2O82−, SO32−. As illustrated in Figure 5b, there were no obvious changes in the absorbance except for H2S, revealing that the present sensing system exhibited excellent

without the utilization of an acidic support or the addition of a second metal showed poor thiotolerance, which weakened the thioresistance of Ru NPs in the catalytic hydrogenation of orange I.30 Na2S donor generally exists in the form of HS− under alkaline condition.24 A number of HS− absorbed on the surfaces of Ru NPs, and the catalytic active sites on Ru NPs were reduced, resulting in the formation HS−-induced catalytic deactivation of Ru NPs.3,29 To validate this, other biological thiols, such as GSH and Cys, were employed to discuss the responses of the absorption of orange I at the same conditions. As shown in Figure 5a, a significant decreased absorption occurred for the control groups and other amino acids without sulfhydryl groups. An obvious absorption at 512 nm for orange I was observed for GSH, Cys and H2S, convincingly suggesting the interaction between Ru NPs and HS−. The different 7916

DOI: 10.1021/acssuschemeng.7b01448 ACS Sustainable Chem. Eng. 2017, 5, 7912−7919

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Figure 5. (a) Absorbance intensities of orange I at 512 nm toward the same concentration of biological thiols and other amino acids without sulfhydryl groups. Inset: corresponding photographs of orange I within 2 min in the presences of Ru NPs and biological thiols/amino acids. (b) Selectivity of the proposed colorimetric assay against Na2S donors and the interfering substances. Inset: the corresponding photographs of orange I within 2 min in the presence of Ru NPs and interfering substances.

Figure 6. (a−e) Visual responses of different concentration of H2S toward fabricated paper strip sensors. (a) Control group of orange under alkaline condition; (b−e) addition of Ru NPs and 100, 10, 1, 0 μM Na2S donors. (f−n) Visual responses of different interfering substances toward fabricated paper strip sensors. f−n, CO32−, HCO3−, NO2−, NO3−, NH4+, SO42−, S2O82−, SO32− and H2S.

paper strip rapidly faded to colorless in the presence of Ru NPs and N2H4 (Figure 6e), attributed to the superior catalytic hydrogenation performances of Ru NPs. Interestingly, with increasing amounts of H2S gas (from Figure 6d to 6b), more catalytic active sites on Ru NPs were deactivated, introducing the varying degrees of color fading. The fabricated paper strips were also applied to study the effect of gases using their dissolved forms. As illustrated in Figure 6f−n, no color changes were observed for ions other than H2S. The favorable selectivity for H2S was well suitable for processing complex sample matrixes for the environmental samples. The fabricated paper strip sensor was appropriate for the specific and reliable colorimetric monitoring H2S with the concentration of above 1 μM in the atmosphere, and has the potential to be a convenient and portable detection kit without the need of sophisticated instrumentation.

selectivity and antijamming capability for the monitoring of H2S in the atmosphere. Analysis of Real Samples and Evaluation of Method Accuracy. The application of the developed colorimetric assay was investigated by detecting H2S in negative Tai lake water. Different amounts of Na2S donors were spiked into negative Tai lake water, and the H2S level was calculated referring to the regression equation in Figure 4c,d. It was reported that the heavy metal ions existed in water could deactivate the catalytic activity of metal catalysts,32−34 but the heavy metal ions would be precipitated by the formation of hydroxide under alkaline conditions, which systematically indicated the accuracy and precision of the developed colorimetric sensor for H2S detection in the polluted water. As demonstrated in Table S1 of the Supporting Information, the recovery for the samples was in the range of 97.5%−102.3%, and the RSD was within 1.9%. Colorimetric Assay of H2S Using Fabricated Paper Strip Sensor. It was clearly seen that Ru NPs depended colorimetric assay of H2S showed laudable advantages against the literature procedures, in terms of response times, sensitivity and selectivity. The proposed colorimetric principle was devoted to fabricate a colorimetric paper strip for H2S gas assay. H2S gas was generated by a stoichiometric reaction between Na2S and diluted H2SO4 (Na2S + 2H+ = H2S↑ + 2Na+).35 The sensing pH was controlled at acidic conditions.2,11,35,36 As demonstrated in Figure 6a, an obvious red color was observed for the paper strips when just orange I was existed under alkaline conditions. However, the red colored

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CONCLUSION In summary, a simple Ru NPs depended colorimetric principle was proposed for the specific and ultrasensitive detection of H2S. Ru NPs were synthesized and exhibited superior catalytic performances, which were 4- and 47-fold higher than that of Pt NPs, Ir NPs. Red-colored orange I could be rapidly degraded to colorless by Ru NPs, but slowly degraded to pink by the introduction of H2S to Ru NPs solution, due to the weak thioresistance of Ru NPs and the poisoning of the catalytic active sites of Ru NPs. The deactivation degrees were evaluated by kinetic rate constants of H2S−Ru NPs triggered catalytic system. Attributing to the superior catalytic activity of Ru NPs 7917

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Detection of Hydrogen Sulfide in Living Cells Based on H2S-Involved Coordination Mechanism. Sci. Rep. 2016, 6, 21951. (9) Jang, J. S.; Kim, S. J.; Choi, S. J.; Kim, N. H.; Hakim, M.; Rothschild, A.; Kim, I. D. Thin-walled SnO(2) nanotubes functionalized with Pt and Au catalysts via the protein templating route and their selective detection of acetone and hydrogen sulfide molecules. Nanoscale 2015, 7, 16417−16426. (10) Zhao, Y.; Liu, L.; Kuang, H.; Wang, L.; Xu, C. SERS-active Ag@ Au core−shell NP assemblies for DNA detection. RSC Adv. 2014, 4, 56052−56056. (11) Zhang, Y.; Shen, H. Y.; Hai, X.; Chen, X. W.; Wang, J. H. Polyhedral Oligomeric Silsesquioxane Polymer-Caged Silver Nanoparticle as a Smart Colorimetric Probe for the Detection of Hydrogen Sulfide. Anal. Chem. 2017, 89, 1346−1352. (12) Zhao, Y.; Yang, Y.; Zhao, J.; Weng, P.; Pang, Q.; Song, Q. Dynamic Chiral Nanoparticle Assemblies and Specific Chiroplasmonic Analysis of Cancer Cells. Adv. Mater. 2016, 28, 4877−4883. (13) Zhao, Y.; Yang, X.; Li, H.; Luo, Y.; Yu, R.; Zhang, L.; Yang, Y.; Song, Q. Au nanoflower-Ag nanoparticle assembled SERS-active substrates for sensitive MC-LR detection. Chem. Commun. 2015, 51, 16908−16911. (14) Gao, Z.; Tang, D.; Tang, D.; Niessner, R.; Knopp, D. Targetinduced nanocatalyst deactivation facilitated by core@shell nanostructures for signal-amplified headspace-colorimetric assay of dissolved hydrogen sulfide. Anal. Chem. 2015, 87, 10153−10160. (15) Deng, H. H.; Weng, S. H.; Huang, S. L.; Zhang, L. N.; Liu, A. L.; Lin, X. H.; Chen, W. Colorimetric detection of sulfide based on targetinduced shielding against the peroxidase-like activity of gold nanoparticles. Anal. Chim. Acta 2014, 852, 218−222. (16) Song, Z.; Wei, Z.; Wang, B.; Luo, Z.; Xu, S.; Zhang, W.; Yu, H.; Li, M.; Huang, Z.; Zang, J.; Yi, F.; Liu, H. Sensitive RoomTemperature H2S Gas Sensors Employing SnO2Quantum Wire/ Reduced Graphene Oxide Nanocomposites. Chem. Mater. 2016, 28, 1205−1212. (17) Zhao, Y.; Luo, Y.; Yang, X.; Yang, Y.; Song, Q. Tunable preparation of ruthenium nanoparticles with superior size-dependent catalytic hydrogenation properties. J. Hazard. Mater. 2017, 332, 124− 131. (18) Yin, A. X.; Liu, W. C.; Ke, J.; Zhu, W.; Gu, J.; Zhang, Y. W.; Yan, C. H. Ru nanocrystals with shape-dependent surface-enhanced Raman spectra and catalytic properties: controlled synthesis and DFT calculations. J. Am. Chem. Soc. 2012, 134, 20479−20489. (19) Ohyama, J.; Sato, T.; Yamamoto, Y.; Arai, S.; Satsuma, A. Satsuma, A. Size specifically high activity of Ru nanoparticles for hydrogen oxidation reaction in alkaline electrolyte. J. Am. Chem. Soc. 2013, 135, 8016−8021. (20) Iqbal, S.; Kondrat, S. A.; Jones, D. R.; Schoenmakers, D. C.; Edwards, J. K.; Lu, L.; Yeo, B. R.; Wells, P. P.; Gibson, E. K.; Morgan, D. J.; Kiely, C. J.; Hutchings, G. J. Ruthenium Nanoparticles Supported on Carbon: An Active Catalyst for the Hydrogenation of Lactic Acid to 1,2-Propanediol. ACS Catal. 2015, 5, 5047−5059. (21) Amirav, L.; Oba, F.; Aloni, S.; Alivisatos, A. P. Modular synthesis of a dual metal-dual semiconductor nano-heterostructure. Angew. Chem., Int. Ed. 2015, 54, 7007−7011. (22) Ruppert, A. M.; Jędrzejczyk, M.; Sneka-Płatek, O.; Keller, N.; Dumon, A. S.; Michel, C.; Sautet, P.; Grams, J. Ru catalysts for levulinic acid hydrogenation with formic acid as a hydrogen source. Green Chem. 2016, 18, 2014−2028. (23) Cui, M.; Zhao, Y.; Wang, C.; Song, Q. Synthesis of 2.5 nm colloidal iridium nanoparticles with strong surface enhanced Raman scattering activity. Microchim. Acta 2016, 183, 2047. (24) Wang, S.; Liu, X.; Zhang, M. Reduction of Ammineruthenium(III) by Sulfide Enables In Vivo Electrochemical Monitoring of Free Endogenous Hydrogen Sulfide. Anal. Chem. 2017, 89, 5382−5388. (25) Ge, J.; He, D.; Bai, L.; You, R.; Lu, H.; Lin, Y.; Tan, C.; Kang, Y. B.; Xiao, B.; Wu, Y.; Deng, Z.; Huang, W.; Zhang, H.; Hong, X.; Li, Y. Ordered Porous Pd Octahedra Covered with Monolayer Ru Atoms. J. Am. Chem. Soc. 2015, 137, 14566−14569.

and the rapid H2S-induced specific response, the developed assay for H2S detection displayed a high sensitivity with a wide linear range of 5−100 nM and a low LOD of 0.6 nM. The proposed principle for colorimetric assay enabled the visual readout with the naked eyes, and showed potential as a novel detection paper strip for point-of-care testing of H2S.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b01448. Photographs of orange I before and after the addition of Ru NPs, UV−vis spectra of orange I at different pH, TEM images of Pt NPs and Ir NPs, table of colorimetric assay of H2S spiked in Tai lake water (PDF)

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AUTHOR INFORMATION

Corresponding Author

*Q. Song. E-mail: [email protected]. ORCID

Qijun Song: 0000-0002-7579-885X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is financially supported by the National Natural Science Foundation of China (21403090), China Postdoctoral Science Foundation (2015M570405, 2016T90417), the foundation of Key Lab of Synthetic and Biological Colloids, Ministry of Education, Jiangnan University (No. JDSJ2015-08 and JDSJ2016-01) and the 111 Project (B13025).

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REFERENCES

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DOI: 10.1021/acssuschemeng.7b01448 ACS Sustainable Chem. Eng. 2017, 5, 7912−7919