Porous Wood Members-Based Amplified Colorimetric Sensor for Hg2+

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Porous Wood Members-Based Amplified Colorimetric Sensor for Hg2+ Detection through Hg2+-Triggered Methylene Blue Reduction Reactions Jun Hai, Fengjuan Chen, Junxia Su, Fu Xu, and Baodui Wang Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b00710 • Publication Date (Web): 08 Mar 2018 Downloaded from http://pubs.acs.org on March 8, 2018

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Analytical Chemistry

Porous Wood Members-Based Amplified Colorimetric Sensor for Hg2+

Detection

through

Hg2+-Triggered

Methylene

Blue

Reduction Reactions

Jun Hai,†a Fengjuan Chen,†a Junxia Su,† Fu Xu,‡ Baodui Wang, †* †

State Key Laboratory of Applied Organic Chemistry and Key Laboratory of Nonferrous

Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou University, Gansu, Lanzhou, 730000, China. ‡

Department of Pharmacy, Lanzhou University Second Hospital, Lanzhou 730000, P. R.

China a

Jun Hai and Fengjuan Chen contributed equally to this work.

ABSTRACT

Wood has attracted increasing scientific interest in the field of green electronics, biological devices, bioenergy and energy storage because of its abundance, low cost, biocompatibility and natural vessel structure. However, its potential application in the important area of environmental monitoring has not yet been effectively explored. In this work, gold nanoparticles (NPs) encapsulated in porous wood (denoted as Au@wood) for highperformance colorimetric detection of Hg2+ in aqueous solution has been constructed. The detection mechanism is based on Hg2+-triggered methylene blue (MB) reduction-assisted signal amplification. In such detection system, Au NPs can be used as a specific identification element for the binding of Hg2+ due to the formation gold amalgam to initiate catalytic activity of gold. The low cost natural wood is introduced to prevent the aggregation of Au

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NPs and increase the contact area between MB and Au NPs in three-dimensional space. MB, as a tracer molecule, enables the output signals to be directly observed by the naked eye. Such detection system exhibited an ultralow detection limit of 32 pM for Hg2+, which is greatly lower than the threshold levels (10 nM) for drinking water and other colorimetric method. The proposed detection system also exhibits high selectivity against other metal ions and works well for environmental water and blood samples. The resultant Au@wood sensor is low cost, easy handling, and convenience, making it an attractive material for point-of-use monitoring of Hg2+ in environmental and biological samples.

Mercury ion (Hg2+) is one of the most hazardous pollutants in the environment and in living organisms. Specifically, pollution by Hg2+ and its derivate can lead to severe damages on the environment and human health.1-2 For example, Hg2+ can be accumulated in human bodies through food and high Hg levels in the environment, which may cause disorder and nonreversible damage to the kidney, brain, and liver, even immune, nervous, and endocrine systems.3-8 Currently, numerous approaches based on electrochemical and optical sensors,9-11 organic chromophores or fluorophores,12-17 conjugated polymers,18 oligonucleotides,19-21 DNAase,22-23 and proteins,24-26 as well as inorganic nanostructures have been established for the sensitive and selective detection of Hg2+ ions.24, 27-28 Unfortunately, most of these methods have the disadvantages of poor water solubility, low selectivity, low sensitivity and complex synthetic process. Therefore, there is an urgent need to establish a simple, fast, sensitive method for the detection of Hg2+ in aquatic ecosystems.


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Recently, a number of colorimetric sensors based on noble metal nanozymes for detection of heavy metal ions like Hg2+ ions have attracted more and more attention due to their distinct variation in color.29-30 Such detection mechanism is based on the mercury-stimulated peroxidase mimetic activity.31-33 Compared with the traditional fluorescence based analysis method, the catalytic based analysis method has certain advantages in detecting stability and resisting the target ability of complex medium interference (i.e., blood). However, to be used popularly, the cost and the sensitivity of current materials still need to be solved. Given the abundance, low cost, biocompatibility and natural vessel structure, wood has been enjoying a resurgence of interest in various advanced applications including green electronics, biological devices, bioenergy and energy storage.34-40 Hardwood, a kind of basswood employed in our study, possesses a complex microstructure with long, partially aligned channels along the growth direction. Such naturally developed hierarchical porous structure not only shows extremely stability and biocompatibility, but also allows nanomaterial disperses uniformly to avoid agglomeration. In addition, the bulky pore size and high surface area further make them applicable for chemical processes. We envisage the application of this material to the carrier of the noble metal nanocatalysts, which not only reduces the cost of the catalyst but also improves the sensitivity of the detection. Toward this goal, we firstly used gold nanoparticles (Au NPs) encapsulated in the wood channels of basswood as chemosensors for effective and selective detection of Hg2+ on the basis of Hg2+-triggered MB reduction-assisted signal amplification (Scheme 1). Au NPs can be used as a specific identification element for the binding of Hg2+ due to the formation gold amalgam to initiate catalytic activity of gold. The long, irregularly shaped wood channels act as a three dimensional (3D) substrate to support the Au NPs. Due to the mesostructure of wood, the Hg2+ and methyl blue solution will get much higher chances to contact with the anchored Au NPs of the wood channels, which is essential for reducing the cost and



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improving the sensitivity of the detection. Upon Hg2+ ions introduction, the formed gold amalgam in wood membrane can catalyze the reduction of MB, mahing the output signals to be directly observed by the naked eye. Additionally, the prepared Au@wood membrane could fast detect Hg2+ in Yellow river water and other samples. Moreover, this Au@wood membrane can be used as a test paper for visual detection of Hg2+ in blood sample.

Scheme 1. Schematic illustration of colorimetric detection of mercuric ion (Hg2+) using Au@wood membrane catalytic reduction of MB.

EXPERIMENTAL SECTION Materials. chloroauric acid (HAuCl4), sodium citrate, NaNO3, KNO3, Hg(NO3)2·H2O, Ca(NO3)·4H2O, Cd(NO3)2·4H2O,

Al(NO3)3·H2O, Fe(NO3)2·9H2O,

Cu(NO3)2·6H2O, Ba(NO3)2,

Ni(NO3)2·6H2O, Fe(NO3)3·9H2O,

Cr(NO3)3·9H2O, Mg(NO3)2·6H2O,

Mn(NO3)2·4H2O, Zn(NO3)2·6H2O, methylene blue (MB), sodium borohydride (NaBH4), were obtained from Sigma Aldrich and used directly. The basswood was received from the Walnut Hollow Company. 13 nm Au NPs were prepared according to the literature.41 Measurements. UV-vis spectra were achieved by a Shimadzu UV-1750 spectrophotometer. TEM measurements were performed by a JEM-2100 instrument. Morphology of Au@Wood membranes was recorded by Field-Emission Scanning Electron Microscope (FE-SEM, FEI, Sirion 200). X-ray photoelectron spectroscopy (XPS) measurements were investigated on a


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PHI-5702 multifunctional spectrometer. XRD measurements were executed on a X-ray powder diffractometer equipped with Cu - K α radiation (λ = 1.540 Å).

Photos were

processed by using Photoshop software (Adobe, CA).

Synthesis of Au@Wood Membrane. The wood slices were immersed in the Au NPs solution (25 nM) for 2 hours, and then the resultant wood membrane was taken out from the solution and dried out at room temperature for another 2 hours.

Synthesis of Au@Wood test paper. A piece of Au@Wood membrane was immersed with 1 µM MB solution for 1 hour, then the resultant wood membrane was dried out at room temperature for another 2 hours.

Preparation of Stock Solutions (1 mM) of Metal Ions and MB Solution. Stock solutions (1 mM) of metal ions (Na+, K+, Ca2+, Mg2+, Al3+, Cr3+, Cd2+, Cu2+, Mn2+, Ba2+, Pb2+, Ni2+, Fe2+, Fe3+, Zn2+ and Hg2+) and anions (SO42-, SO32-, NO3-, NO2-, CO32-, PO43-, HPO42-, Cl-, AcO- and HCO3-) were prepared in ddH2O.

Hg2+ Assay Protocols. For Hg2+ detection, Au@Wood membrane containing 1 µM Au NPs was incubated in deionized water. Then, the Hg2+ solution with several concentrations was added to the above mixture. After 50 µL of MB solution (1 µM) was injected into the mixture, a freshly prepared NaBH4 solution (50 µL, 0.5 mM) was added to the above mixture. The change of absorption peak of the MB solution is tracked by UV-vis spectra, and the color change of the solution is captured by Nikon j5 digital camera. In addition, colorimetric detection different concentrations of Hg2+ in wastewater and whole blood samples were carried out using the above method.

RESULTS AND DISCUSSION Characterization of Au@Wood membrane.



Figure 1. (A) Photo images of natural wood and the Au@wood membrane. (B) TEM image of Au NPs. (C-F) The SEM images of the wood membranes before (C, D) and after (E, F) encapsulating Au NPs. (G) TEM image of Au@Wood membrane. (H) The HRTEM image exhibits the (111) lattice plane of Au with an interplanar distance of 0.24 nm. Inset shows the SAED pattern of the Au@wood membrane. (J) XRD of wood, Au NPs and Au@Wood membrane. (K-O) Dark field of STEM and element mapping images of Au@Wood membrane.

Figure 1A shows digital images of natural wood and the Au@wood membrane. Figure 1B shows that Au NPs with ~13 nm have been successfully prepared (Figure S1). The morphology and microstructure of the wood membranes before and after encapsulating Au NPs are characterized by scanning electron microscopy (SEM), as shown in Figure 2C-F. Natural basswood shows a unique 3D porous structure with massive channels along the wood


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growth direction (Figure 1C and D). After encapsulating Au NPs, the multichanneled 3D porous structure can be well preserved (Figure 1E and F). Meanwhile, the smaller pits on the inside surface of wood channels allows materials transport in the radial directions in the wood trunk. In order to verify that Au NPs were present in the 3D wood, transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) were used. As shown in Figure 1G, Au NPs were observed in wood, and the measured lattice fringes correspond to a spacing of 0.24 nm, which match well with the expected spacing of the (111) plane of the Au (Figure 1H). Figure 1J shows that the as-synthesized Au@wood membrane had two sets of diffraction peaks. Peaks around 2θ = 15.8°, 21.6°, and 34.2° correspond to cellulose crystals with characteristic assignments of (110), (200), and (004) planes, respectively. Peaks at 38.1°, 44.4°, 64.6° and 77.7° were assigned to the (111), (200), (220), and (311) planes of Au (JCPDS no. 89-3697). Au NPs exist in wood was further confirmation by elemental mapping. As shown in Figures 1K-O, Au NPs are evenly distributed in wood, which was consistent with the energy-dispersive X-ray (EDX) (FigureS2). In addition, the X-ray photoelectron spectrometer (Figure S3) also indicated that there existed the zero state gold. Au@Wood membrane shows the maximum absorption peak at 524 nm, which is the same with Au NPs (Figure 2A). Moreover, in the Fourier transform infrared spectroscopy (FTIR) (Figure S4), the additional absorption peaks around 557 cm-1 are assigned to the Au-O stretching modes,42 indicating the interaction between hydroxyl groups of the cellulose/hemicellulose and the gold atoms. Furthermore, inductively coupled plasma (ICP) analysis results also confirmed that the Au NPs encapsulated in wood membrane with loading amount of 5.0 wt %.



Figure 2. (A) UV-vis absorption spectra of Au NPs, Au @Wood, and Au@Wood in the presence of Hg2+. (B) High resolution XPS spectra of Hg 4f in Au@Wood after being treated with Hg2+. (C-H) Dark field of STEM and element mapping images of Au@Wood in the presence of Hg2+.

As well know, in the presence of Hg2+, Au NPs are easy to combine with Hg2+ to form gold amalgam. To confirm the formation of gold amalgam in Au@wood members, UV-vis absorption spectra, SEM image, and XPS were used. As shown in Figure 2A, the absorption peak of Au@wood considerably blue-shifted to around 522 nm when adding the Hg2+. Moreover, XPS (Figure 2B and S5) and elemental mapping (Figures 2C-H) indicated that gold amalgam was formed in Au@wood membrane, and Hg0 state was present on the surface of Au@wood membrane, which was confirmed by two binding-energy peaks at 99.79 eV (assign to Hg 4f7/2) and 103.89 eV (assign to Hg 4f5/2). Selectivity and sensitivity of Au@wood membrane for detecting Hg2+


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As shown in Figure 3, the wood, Au NPs, and Au@wood did not exhibit any catalytic activity toward reduction MB in the absence of Hg2+. However, the addition small amount of Hg2+ improves the catalytic performance of the Au@wood and Au NPs. In addition, the Au@wood exhibited higher mercury stimulated activity than that of alone Au NPs, which is due to the mesostructure of wood that provides much higher chances to contact with the anchored Au NPs of the wood channels.

Figure 3. UV-vis absorbance change of MB solutions at 662 nm catalyzed by Wood, Au NPs, and Au@Wood in the absence and presence of Hg2+.

To evaluate the sensitivity of Au@wood for detection of Hg2+; UV-vis spectra were achieved by the adding different concentrations of Hg2+ (0-28 nM). As shown in 4A, the absorbance value of MB was constantly decreased following the increase of Hg2+ concentration. Even at 2 nM Hg2+, the change of UV-vis absorbance was evidently detected by the UV- spectrometer, and UV-vis absorbance value of the MB solution were decreased to 98 %, which indicating an ultrasensitive response to Hg2+. Figure 4B illustrated the linear plot of (A0-A) against different Hg2+ concentration (1 nM to 28 nM), the colorimetric value was significantly increased. The detection limit of Hg2+ in water is 32 pM, which is greatly lower than the threshold levels (10 nM) for drinking water. In addition, the detection limit of



Au@Wood toward Hg2+ is lower than that of Au NPs (2.05 nM, Figure S6) and other colorimetric method.15, 27, 29 The relative high sensitivity was due to the encapsulation of Au NPs into wood, which could enhance the contact area between catalyst and substrates, indicating the pivotal role of wood in sensing and recognizing of Hg2+.

Figure 4. (A) Absorption intensity changes of the mixed MB, Au@Wood and NaBH4 solution caused by various concentrations of Hg2+. Inset: The photographs at various concentrations of Hg2+. (B) The plot of the colorimetric (A0-A) against Hg2+ concentrations. The inset shows the linear least-squares regression of (A0-A) against Hg2+concentrations (0-10 nM).

The selectivity of Au@wood membrane for Hg2+ was evaluated by adding 10-fold of other metal ions including Na+, K+, Ca2+, Mg2+, Al3+, Cr3+, Cd2+, Cu2+, Mn2+, Ba2+, Pb2+, Ni2+, Fe2+, Fe3+, Zn2+, and Ag+ at a concentration of 0.1 mM. As shown in Figure 5A, the absorbance of MB was practically similar in the presence of other ions. Furthermore, in the presence of 10 equiv of various other ions, 1 equiv of Hg2+ still caused a significant decrease of absorbance at 662 nm (Figure 5B). These results indicate that Au@wood membrane can specifically recognize Hg2+ over other metal ions. Importantly, this high selectivity can be visualized with the naked eye (Figure 5C). We also investigate the effect of other normal anions, such as SO42-, NO3-, NO2-, CO32-, PO43-, Cl-, AcO- and HCO3-. As shown in Figure S7, except for SO42-, CO32-, PO43- influence detection (due to formation of precipitation with Hg2+), other


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anions have no effect on the detection results. In addition, this detection system could be performed in abroad pH values (from 4 to 11) (Figure S8), showing its potential industrial applications.

Figure 5. (A) Absorption intensity changes of MB solution (1 mM) upon addition of Na+, K+, Ca2+, Mg2+, Al3+, Cr3+, Cd2+, Cu2+, Mn2+, Ba2+, Pb2+, Ni2+, Fe2+, Fe3+, Zn2+, Ag+ and Hg2+ (0.1 µM for Hg2+, 0.1 mM for other metal ions). (B) Absorption changes (662 nm) of MB+ Au@Wood + NaBH4 upon addition of 1 equiv of Hg2+ and 10 equiv of various metal ions. Black bar: MB+ Au@Wood + NaBH4 + metal ions; Red bar: MB+ Au@Wood + NaBH4 + metal ions + Hg2+. (C) The photographs of MB+ Au@Wood + NaBH4 upon addition of various metal ions.

Practical Application of Au@Wood Membrane for Detecting Hg2+ To estimate the applicability of the Au@Wood membrane detecting Hg2+ in real samples, we test tap water, deionized water, and Yellow river water samples containing different concentrations Hg2+. Figure 6 shows the colorimetric assay results for all above samples in the presence of Hg2+, which is significantly lower relative to that of increasing Hg2+ concentration. Moreover, as shown in Figure 6, there was no obvious difference in these three samples (Yellow river water, tap water and deionized water), suggesting that Au@Wood



membrane can detect Hg2+ without being affected by the other interfering metal ions and other organic contaminants. Additionally, to demonstrate the feasibility of Au@Wood membrane in practical applications, we designed a recovery experiment via spiked tap water, Yellow river water, and deionized water samples. Table 1 demonstrated the recovery of Hg2+ solution with different concentrations for all the samples was statistically near to 100% (range from 95.7% to 103%). All these results suggested that the Au@Wood membrane will be stable for detection of Hg2+ in any reasonable assay conditions, and showed a great potential of application in real water detection.

Figure 6. The plot of the absorbance against the concentration of Hg2+ in various water samples.

Au@Wood Membrane as Test Paper for Visual Detection of Hg2+ A test paper prepared by Au@wood membrane has been developed for visual detection of Hg2+ in aqueous solution. A 5 × 5 mm of Au@wood membrane was immersed in MB solution (1 µM) for 1 hour, then the Au@wood membrane immobilized MB (denote as MB/Au@wood) dried out at 25 0C for 2 hours. For Hg2+ detection, different concentration of Hg2+ was dropped onto the test paper. As shown in Figure 7A, an obviously distinguishable


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color against the original background was appeared, and a minimum concentration of ∼0.2 µM for Hg2+ could be detected with the naked eye. Table 1. The recovery results of tap water, deionized water, and Yellow river water samples containing different concentrations Hg2+ measured by UV-vis spectrometry and ICP mass spectrometry. Hg2+ concentration (nM) Colorimetric mean ICP-MS mean Sample Yellow river water 1 Yellow river water 2 Yellow river water 3 Tap water 1 Tap water 2 Tap water 3 DI water 1 DI water 2 DI water 3

Spiked 3.0 6.0 9.0 3.0 6.0 9.0 3.0 6.0 9.0

Found 2.87 ± 0.12 5.87 ± 0.10 8.89 ± 0.09 2.91 ± 0.06 5.98 ± 0.11 9.07 ± 0.07 3.09 ± 0.06 6.10 ± 0.08 9.06 ± 0.12

Recovery (%) 95.7 ± 3.12 97.8 ± 1.50 98.8 ± 0.10 97.0 ± 2.65 99.7 ± 1.21 100.8 ± 0.98 103 ± 2.23 101.7 ± 1.50 100.7 ± 0.84

Found 2.97 ± 0.01 6.03 ± 0.03 8.97 ± 0.06 3.01 ± 0.06 6.05 ± 0.08 8.98 ± 0.04 2.99 ± 0.05 5.98 ± 0.10 9.05 ± 0.13

Recovery (%) 99.0 ± 0.85 100.5 ± 0.50 99.7 ± 0.69 100.3 ± 0.53 100.8 ± 0.55 99.8 ± 0.61 99.7 ± 0.44 99.7 ± 0.50 100.6 ± 0.82

Figure 7. (A) The colorimetric images of MB on Au@wood membrane upon addition of Hg2+ in ddwater. (B) The colorimetric images of the Au@Wood test paper upon addition of different concentrations of Hg2+ in blood sample.

Moreover, we performed an experiment that MB/Au@wood test members were immersed in blood sample with different concentration of Hg2+, the result show clearly that absorbance value of MB/ Au@wood test members was constantly decreased with the increase of Hg2+ concentration (Figure S9), and the color of the members is getting lighter and lighter with the



addition of Hg2+ (Figure 7B). All of this evidence proved that Au@wood membrane can be used for the accurate detection of Hg2+ in real samples.

CONCLUSION In conclusion, for the first time, we have introduced a simple and scalable material, porous 3D Au@wood composite, for high-performance colorimetric detection of Hg2+ in aqueous solution based on Hg2+-triggered MB reduction-assisted signal amplification. Thanks to the irregularly shaped Au-wood channels, the Hg2+ and MB get much higher chances to contact with the anchored Au NPs in 3D space. Thus, our protocol is able to achieve ultrasensitive detection of Hg2+ assay, with a detection limit of 32 pM, meeting the 10 nM guidelines issued by EPA6 for inorganic mercury in drinking water. Moreover, the prepared Au@wood membrane can also be used for efficient and sensitive detection of Hg2+ in environmental and biological samples. Given the abundance and unique structure of the wood, our success in applying wood members-based amplified colorimetric sensor to mercury monitor enables bioanalysis and environmental monitoring in the future.

ASSOCIATED CONTENT Supporting Information Characterizations, Supporting Figures and Tables are available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected].

ACKNOWLEDGMENTS


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The work was supported by the National Natural Science Foundation of China (21671088, 21431002, and 21501080), Fundamental Research Funds for the Central Universities (lzujbky-2017-105). We wish to thank the Electron Microscopy Centre of Lanzhou University for the microscopy and microanalysis of our specimens.

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