Newly Designed Amperometric Biosensor for Hydrogen Peroxide and

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A Newly Designed Amperometric Biosensor for Hydrogen Peroxide and Glucose Based on Vanadium Sulfide Nanoparticles Arpita Sarkar, Abhisek Brata Ghosh, Namrata Saha, Gopala Ram Bhadu, and Bibhutosh Adhikary ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.8b00076 • Publication Date (Web): 13 Feb 2018 Downloaded from http://pubs.acs.org on February 14, 2018

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ACS Applied Nano Materials

A Newly Designed Amperometric Biosensor for Hydrogen Peroxide and Glucose Based on Vanadium Sulfide Nanoparticles Arpita Sarkar,a Abhisek Brata Ghosh,a Namrata Saha,a Gopala Ram Bhadub and Bibhutosh Adhikary*a a

Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur,

Howrah 711 103, West Bengal, India b

Department of Analytical Science, Central Salt & Marine Chemicals Research Institute, Gijubhai, Badheka Marg, Bhavnagar 364002, Gujarat, India

Corresponding Author *E-mail: [email protected]

ACS Paragon Plus Environment

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Abstract In the present work, we describe a facile, green and template free solvothermal fabrication of vanadium sulfide nanoparticles (VS2 NPs) and their application for the electrochemical detection of hydrogen peroxide (H2O2) and glucose. The morphology and composition of as prepared samples were well characterized by powder X-ray diffraction (XRD), energy dispersion spectroscopy (EDS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-Vis spectroscopy and Brunaur-Emmett-Teller (BET) surface area measurement. Due to their interesting electrochemical responses toward hydrogen peroxide, a novel nonenzymatic electrochemical sensor for H2O2 and glucose detection has been proposed based on VS2 NPs modified glassy carbon electrode. The modified electrode showed excellent electrochemical performance for selective and sensitive nonenzymatic detection of H2O2 in a broad concentration range of 0.5 µM‒3.0 mM, with a wide linear range of 0.5 µM–2.5 mM and a lower detection limit of 0.224 µM. The newly developed sensor also displayed high sensitivity (41.96 µA mM-1) towards detection of glucose with a broad linear range of 0.5 µM–3 mM. The as fabricated sensor also showed very high sensitivity, excellent reusability, long term stability and negligible interference ability. Moreover, the synthesized nanoparticles were applied for H2O2 and glucose detection in real samples, signifying their potential application in routine H2O2 and glucose analysis. The present study reveals that as prepared VS2 NPs are promising for electrochemical hydrogen peroxide and glucose sensing and other biological applications.

Keywords: VS2 NPs, fabrication, modified electrode, biosensing, amperometric biosensor.


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Introduction Recently rapid, selective and accurate determination of hydrogen peroxide (H2O2) and glucose in biological systems have attracted considerable interest in the field of biomedicine, biological analysis, environmental protection , food security etc.1,2 Hydrogen peroxide is a very simple compound in nature but plays great roles in pharmaceutical, industrial, environmental, clinical and food manufacturing applications.3-5 Moreover, some classic biomedical reactions catalyzed by enzymes such as lactose oxidase, glucose oxidase, urease, alcohol oxidase , sarcosine oxidase, cholesterol oxidase etc can also generate H2O2 as a side product. It is also worth mentioning that H2O2 is a strong oxidizer and recognized as one of the major risk factors in progression of different kinds of disorder in body, such as Atherosclerosis, renal disease, Parkinson’s disease, Alzheimer’s disease and cancer.6-10 On the other hand, an increase amount of glucose in blood creates diabetes mellitus which can bring about serious complications, such as blindness, kidney failure, strokes etc.11 Therefore, development of selective and sensitive methods for H2O2 and glucose detection is of practical importance for industrial, biomedical and academic purposes. In the last few years, several measurement techniques for the detection of H2O2 and glucose have

been

explored,

electrochemical methods

including 17,18

fluorimetry,12,13chromatography,14spectrometry,15,16

etc. However, most of them are time consuming, complex and

costly. In comparison, the electrochemical technique was given tremendous attention due to its fast response, low cost, high sensitivity, simplicity and good efficiency.19,20 Furthermore, catalytic reduction of hydrogen peroxide by horseradish peroxidase (HRP), a natural enzyme, was found to be an popular technique earlier, though it has severe disadvantages.21,22 To overcome these obstacles, more efforts have been made in the aspect of artificial nonenzymatic

hydrogen

peroxide

and

glucose

sensors.23,24 In particular,

nanomaterials,25,26 metal nanoparticles,27-29 metal oxide/sulfide semiconductors


carbon 30-34

and


graphene-based nanomaterials

35-37

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have been largely employed because of their suitable

biocompatibility, low cost preparation, unique catalytic properties and good stability. In recent few years, transition-metal dichalcogenides (TMDs), such as WS2, MoS2, VS2 etc have been well recognized as a new paradigm in chemistry for their unique layered structure.38-41 Among those TMDs, VS2 NPs have been considered to have immense potential for applications such as spintronics42-44, energy storage devices etc

45-47

due to their highly

conductive property. Moreover, VS2 is cheap and source abundant. However, numerous practical difficulties in synthesizing of VS2 NPs, hampered research involving the material in the past.48 With the development of simple synthetic methods, along with the rising attention in transition metal dichalcogenides (TMDs), has motivated for a renewed attempt to continue novel research on vanadium sulfide.49 Recently, other TMDs like WS2, MoS2 NPs have been studied for H2O2 and glucose sensing.50 However, according to our knowledge no one has yet studied the sensing property of VS2 NPs. The high conductive property and cheap cost of the VS2 NPs encouraged us to study their electrochemical sensing behavior for H2O2 and glucose. Herein, we report a facile synthetic protocol for the formation of VS2 NPs through a simple solvothermal decomposition of the vanadium dithiocarboxylate complex. VS2 NPs modified glassy carbon electrode was then fabricated for the detection of H2O2 and glucose. In both cases promising results have been found. The results showed that as prepared VS2 NPs could be a novel material for creation of selective and sensitive electrochemical sensor for H2O2 and glucose detection.


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Experimental section Chemicals and materials Vanadium pentoxide (V2O5), acetyl acetone, triethylenetertamine (TETA), hydrogen peroxide (30%), nafion were purchased from Sigma-Aldrich. Cyclopentanone, Carbon disulfide (CS2), ammonia were purchased from Spectrochem Pvt Ltd. Distilled deionized water (DDW), methanol, toluene, diethyl ether and acetonitrile were used as received. Synthesis of the [VO(acda)2] complex The ligand Hacda (2-aminocyclopentene-1-dithiocarboxylic acid) and VO(acac)2 were synthesized according to the previously reported methods.51,52 A solution of Hacda (0.2 mmol) in methanol was added to a methanolic solution of VO(acac)2 (0.1 mmol) at room temperature, with stirring. On addition, a reddish brown precipitate was formed immediately. The stirring was continued for 30 min. After which the resulting product was filtered, washed with methanol and finally dried over calcium chloride. Yield- 465 mg (75 o/o). Anal. (C12H16VN2S4O) Calc.: C, 38.00; H, 4.35; N, 7.62. Found : C, -

37.59; H, 4.17; N, 7.31. FT-IR (KBr pellet, cm 1): 3365(w, br) ,3292 (w, br), 2938 (w), 1612 (s), 1468 (s), 1324 (w), 950 (m), 806 (m) (Figure S1). UV-Vis [in CH3CN, λmax, nm (ε / M-1 cm-1)] 399 (Figure S2). The synthesis of VS2 NPs, the fabrication method of VS2/nafion-modified glassy carbon electrode (VS2/Nf/GCE), experimental details of electrochemical activity towards H2O2 and details of physical measurements are provided in the supporting information.

Results and discussion The VS2 nanoparticles were synthesized by solvothermal decomposition of [VO(acda)2] complex in TETA at 220°C (Scheme S1).The TGA curve of VO(acda)2 complex is shown in Figure S3. The complex got decomposed between 48 and 710°C indicating the formation of VS2 NPs. The curve shows a 29.67 wt% residue at 710oC, resulting in the formation of VS2



NPs. The given weight percentage residue by TGA (29.67 wt %) is in well agreement with the calculated weight percentage of VS2 NPs (30.01 wt %). Structural characterization The phase purity and crystallinity of the synthesized VS2 NPs were examined by X-ray diffraction (XRD) technique. The major diffractions were observed from (001), (100), (101), (102), (110), (201) planes whose 2θ values match well with the standard JCPDS values of file no 36-1139 (Figure 1). In Figure 1, strong intense peaks were observed, which indicates crystalline nature of the material. On the other hand, the broadening of the peaks indicates the presence of smaller-sized particles. Using the Debye-Scherrer equation [D= 0.9λ/(βcosθ), λ =1.540599 Å], the average crystallite size of the VS2 NPs was estimated to 9.4 nm. The XPS core-level spectrum of VS2 NPs was investigated and shown in Figure S4. The obtained two peaks with binding energy 515.8 and 524.6 eV can be attributed to V (IV) 2p3/2 and V (IV) 2p1/2.41,53 In addition, the EDS elemental study shows that the synthesized nanoparticles are composed of vanadium (V) and sulfur (S) (Figure S5).

Figure 1. Powder XRD patterns of VS2 NPs.


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The morphology of VS2 NPs was carried out by SEM measurement. Figure S6 shows the formation of spherical nanoparticles with average diameter of 8.2 nm. Furthermore, the structural characterization of VS2 NPs were carried out using transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), size distribution curve and selected area electron diffraction pattern (SAED) which are presented in Figures 2A, 2B, 2C and 2D respectively. Figure 2A shows that the synthesized VS2 NPs are spherical in shape. On the other hand, Figure 2B shows the size distribution of the synthesized nanoparticles, which ranges from 6.0 to 12 nm with an average diameter of ~ 8.1 nm. The SAED patterns demonstrate a set of concentric rings that can be indexed to (001), (101) and (110) diffraction planes of VS2 NPs (Figure 2C). From HRTEM images (Figure 2D) lattice fringes of the nanocrystals can be observed, which suggest excellent crystalline nature of VS2 NPs. From Figure 2D it is clear that the surface morphology of VS2 NPs is single crystalline with a lattice fringe spacing of 0.249 nm corresponding to (101) plane.

(A)

(B)

(C)

(D)

(001) (101) (110)


(0.249 nm) (101)


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Figure 2. (A) TEM image (B) size distribution curve from Dynamic Light Scattering spectroscopy (DLS) (C) SAED pattern and (D) HRTEM image of VS2 NPs. Optical properties UV-Vis spectroscopy is an important tool to reveal the optical properties of the semiconducting materials. Figures S7A and S7B show the UV-Vis absorption spectrum and the corresponding Tauc’s plot of the VS2 NPs, respectively. Using the Tauc’s relation [(αhυ)1/2 vs hυ]54, the band gap energy (Eg) of VS2 NPs can be evaluated (Figure S7B) and is found to be 2.22 eV. A typical nitrogen adsorption-desorption isotherm (BET) for VS2 NPs is shown in Figure S8 and the specific surface area of VS2 NPs is found to be 17.89 m2 g−1. Electrochemical sensing of H2O2 The electrochemical impedance spectroscopy (EIS) of the VS2/nafion modified glassy carbon electrode (VS2/Nf/GCE) was studied to show the electrode performance of the particles. Figure 3 displayed the Nyquist plots of VS2/Nf/GCE and bare GCE under open circuit potential conditions. A characteristic semicircle has been obtained in both cases indicating a single charge transfer process taking place between electrolyte and working material. From Figure 3, it can be seen that the diameter of the semicircle

is decreased in case of

VS2/Nf/GCE (Figure 3B) compared to bare GCE (Figure 3A) which indicates the increase in the available surface area in synthesized material and less obstructions in the electron transfer process. Therefore, VS2/Nf/GCE has been chosen as the working electrode for further investigations on sensing properties.

(A) (B)


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Figure 3. Nyquist plots of (A) bare GCE and (B) VS2/Nf/GCE. Furthermore, the effect of solution pH (4.5 to 8.0) on the electrocatalytic activity of the VS2/Nf/GCE was studied under similar conditions. The reduction peak current increased steadily and the highest response was observed at pH ~7.4 (Figure S9). Hence, pH 7.4 was chosen in subsequent experiments to obtain maximum sensitivity. Moreover, another important factor to the electrochemical response is the concentration of the electrocatalyst on the modified electrode surface.55 The effect of the concentration of VS2NPs on the modified electrode surface was investigated and given in the Supporting Information (Figure S10A and S10B). From Figure S10B, it was observed that when the concentration of VS2NPs was 2.0 mg mL1, the modified glassy carbon electrode showed maximum response. In order to obtain highest sensitivity, 2.0 mg mL−1 was selected for fabrication of the modified electrode. The inherent electrochemistry of VS2 NPs was studied by cyclic voltammetric (CV) experiments in cathodic and anodic scan directions over the range of ± 2.0 V. Figure S11 shows that the synthesized VS2 NPs exhibit an oxidation peak ≈ + 1.4 V and a reduction peak at ≈ -1.4 V during initial anodic as well as cathodic scan. It was observed that the reduction peaks in third and second scan emerges after oxidation process which indicates that the electroactive moieties of VS2 NPs are in reduced state.41 Furthemore,

CV was studied in order to investigate the electrochemical sensing

behavior of the VS2/Nf/GCE electrode with successive addition of H2O2 over the range of 20, 40 and 60 µM in a pH 7.4 PBS solution at scan rate of 0.1 V s-1. It was observed that no obvious redox peaks appeared in case of bare GCE (curve a) and Nf/GCE (curve b) without addition of H2O2 (Figure 4). The cathodic peak current at -0.75 V increased significantly (curves c, d and e) with addition of H2O2, which indicate an obvious electrocatalytic reduction of H2O2.56 The possible mechanism could be expressed as follows: At first, V(IV) was



oxidized to higher state V(V) by H2O2 and then V(V) would be electrochemically reduced at the electrode surface and regenerated as V(IV) (Scheme S2).57

Figure 4. CV curves of (a) bare GCE (b) Nf/GCE and (c, d, e) VS2/Nf/GCE upon successive addition of H2O2 to 0.1 M PBS. In addition, the diffusion-controlled electrochemical behavior of VS2/Nf/GCE was studied by varying the different scan rates from 20 to 180 mVs-1 (Figure 5A). The reduction peak current increased linearly with the square root of the scan rate (Figure 5B), indicating that the electrochemical reaction may be a diffusion-controlled process. From the above results it can be proposed that VS2 NPs can be used as a superior electrochemical sensor for H2O2 detection. (A)

(B)


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Figure 5. (A) CV plots of the VS2/Nf/GCE in 0.1 M PBS in the presence of 20 µM H2O2 at different scan rates: (a) 20, (b) 40, (c) 60, (d) 80, (e) 100, (f) 120 (g) 140 (h) 160 (i) 180 mV s−1, respectively. (B) The linear relationship between the reduction peak current and the square root of scan rates of VS2/Nf/GCE in 0.1 M PBS. Amperometric responses of the VS2/ Nf/GCE to H2O2 To demonstrate the efficiency of the VS2 NPs as a biosensor, typical steady state amperometic response of the synthesized material was studied. Figure S12 shows the effect of the operating potential on the amperometric response of the VS2/Nf/GCE to H2O2. The maximum current response was observed at -0.75 V while varying the operating potential from -0.20 to -0.90 V. Therefore, the quantitative estimation of H2O2 in 0.1 M PBS (pH 7.4) at -0.75 V was carried out using amperometric technique with VS2/Nf/GCE electrode under similar experimental conditions. Figure 6A displays the typical amperometric responses of the VS2/Nf/GCE to successive addition of H2O2 in 0.1 M PBS (pH 7.4) at -0.75 V. From Figure 6A, it is clear that, with an aliquot addition of H2O2 the current raised sharply and steady state was reached within few seconds. This result demonstrates an excellent electrocatalytic performance of the VS2/Nf/GCE electrode. Figure 6B shows the current response plot against H2O2 concentration in a wide range (0.5 µM−3.0 mM). The current response at the VS2/Nf/GCE electrode is linearly related to H2O2 concentration in the range of 0.5 µM - 2.5 mM (Figure 6B), with a correlation coefficient of 0.99628. It is interesting to note that, the linear range for the VS2/Nf/GCE is much wider than 0.5-150 µM for FeS/GC,58 1.76 -139 µM for NCNT/GC,59 10 µM - 1.5 mM for MnO2/Nafion/GC, 601 µM - 1.9 mM for CdS/GC 61 and several recently reported sensors.62,63



(A)

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(B)

Figure 6. (A) Amperometric responses of the VS2/Nf/GCE upon successive additions of various concentration of H2O2. Inset: magnified curve; (B) The linear calibration curve in the H2O2 concentration range of 0.5− 2500 µM. Inset: magnified linear region from 0 to 200 µM. This outstanding value of the non enzymatic H2O2 sensor lies in its high sensitivity and super low detection limit. The sensitivity and the detection limit were estimated to be 37.96 µA mM-1 and 0.224 µM (S/N = 3) respectively (Figure 6B). The linear range and detection limit for the VS2/ Nf/GCE are comparable or even superior to previous H2O2 electrochemical sensors, as summarized in Table S1. By comparing with the previous reported literature, we have found that the VS2/Nf/GCE demonstrates attractive performance as a hydrogen peroxide sensor and can be helpful in biosensing devices. Electrochemical sensing of glucose On the basis of the above performance for hydrogen peroxide sensing, VS2/Nf/GCE was further applied to investigate the detection and quantification of glucose using CV and CA techniques. Figure 7 presents the CV plots of VS2/Nf/GCE by addition of various concentration of glucose in 0.1 M PBS (pH 7.4). From Figure 7 it is clear that the peak current at -0.75 V increased with successive addition of glucose (20, 40, 60, 80 and 100 µM)


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which indicates that the VS2/Nf/GCE electrode is extremely sensitive to the concentration of glucose. This study matches well with some of the previously reported sensors.56, 64

Figure 7. CV curves of (a) VS2/Nf/GCE without glucose and (b, c, d, e and f) upon successive addition of glucose to 0.1 M PBS. Furthermore, the quantitative detection of glucose was made by recording the amperometric response of the VS2/Nf/GCE sensor with successive addition of glucose to a 0.1 M buffer solution under similar optimized experimental conditions. Figure 8A reveals that the prepared biosensor exhibited a rapid increase in current response with the change of concentration of glucose from 0.5 µM to 5 mM. The VS2/Nf/GCE reached 94 % of steady state within 5 s which suggests a good electron transfer electrocatalytic process. The calibration curve (Figure 8B) shows a linear range of 0.5 µM to 3 mM with a detection limit of 0.211 µM (S/N = 3) and the sensitivity is found to be 41.96 µA mM-1. The obtained sensitivity (41.96 µA mM-1) is much better than porous Au electrode (11.8 µA mM−1 cm−2),65 mesoporous Pt electrode (9.6 µA mM−1 cm−2),66 Pt–Pb alloy nanoparticles-MWCNTs/GCE (17.8 µA mM−1 cm−2)67 and many other reported materials.68 The broad linear range of the synthesized biosensor is due to the large specific surface area of VS2 NPs (17.89 m2 g−1) which



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promotes better reaction and adsorption of glucose.69 The high sensitivity and fast response may be due to the super catalytic and promoted electron transfer effects afforded by the VS2 NPs. Interestingly, the synthesized biosensor is not only cheap but also better than the many previously reported glucose based biosensors, as shown in Table 1.

(A)

(B)

Figure 8. (A) Amperometric responses of the VS2/Nf/GCE upon successive additions of various concentration of glucose. Inset: magnified curve; (B) The calibration plot of VS2/Nf/GCE with successive addition of glucose in 0.1 M PBS. Table 1. The comparison of glucose determination with differently modified electrodes. Electrode

Detection limit (µM)

Au/polyvinylpyrrolidone/PAN GOx/AuNPs/PAni/GC Co3O4 nanofibers/nafion/GCE GOx/grapheme/PANI/Au GOx/MOFs/PtNPS CuO NPs MWCNTs-COOH-P2AT-AuNPs CNT-Ni-GCE NiO/Ni foam VS2/Nf/GCE

10 0.5 0.97 0.6 5 0.21 3.7 2 6.15 0.211

Linear range (µM) 0.05-2250 0.001-800 up to 2400 0.004-1120 0.005-1400 0.77-2000 100-3000 5-2000 18-1200 0.5-3000


Reference 70 71 72 73 74 75 76 77 78 In this work

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Selectivity, stability and reproducibility An important characteristic for hydrogen peroxide and glucose biosensors is their antiinterference property which probe selective response of the sensor in presence of other interfering species. Such an anti-interference ability by the amperometric method is shown in Figure S13 using L-cystyne (L-cys), uric acid (UA) and ascorbic acid (AA), which are the general electroactive interfering substances for H2O2 and glucose biosensors. As shown in Figure S13, no significant current responses for UA, AA and L-cys were observed compared to those of hydrogen peroxide and glucose. The size of the VS2 NPs is too small to allow bigger molecules (such as UA, AA or L-cys) to pass through; hence, VS2 NPs show significant anti- interference properties.79 In addition, the stability and reproducibility of the VS2/Nf/GCE were studied by adding a fixed amount of glucose (20.0 µM) to PBS (0.1M) solution. The relative standard deviation (RSD) was observed to be 3.4%, which decreased to 2.7 % after five repeat measurements using the same electrode. This result demonstrates that the determination was repeatable and the fabrication procedure was extremely reproducible. The long-time stability of the VS2/Nf/GCE was further investigated by testing its current responses over 30 days, which retained ~92% of its original signal (Figure S14), suggesting its significant long-time stability. Real samples sensing A literature survey reveals that a substantial amount of H2O2 is excreted in normal human urine.80 In addition, commercial hair dye also contains a considerable amount of H2O2. Hence, an effort has been made to detect the concentration of H2O2 in excreted human urine as well as a commercial hair dye. The aqueous solution of these selected samples were diluted to proper concentrations with 0.1 M PBS. The data found by permanganometric titration of the same samples have been compared and displayed in Table S2.



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In addition to confirm the reliability of the prepared glucose sensor, VS2/Nf/GCE was used to determine glucose in human blood serum sample by standard method. The experiment was carried out by diluting the serum samples with 0.1 M PBS in order to avoid the interference. It is observed from Table 2 that the measured concentrations of glucose in human blood are very close to the obtained values from a pathological laboratory and the recovery factors are very satisfactory. Table 2. Determination of glucose in human blood serum. Samples Determined values (mM) 1 4.57 2 3.92 3 5.26

Reference values (mM) 4.68 3.86 5.14

RSD (%) 3.3 3.7 4.1

Recovery 99.78 99.12 98.9

Conclusions In conclusion, VS2 nanoparticles have been successfully prepared from a dithiocarboxylate complex of vanadium by a simple solvothermal decomposition process. The synthesized VS2 NPs exhibited high electrochemical response toward H2O2 and glucose, based on which a sensitive and selective electrochemical sensor has been proposed and applied for H2O2 and glucose detection with acceptable accuracy. The above study complements in the research field of nonenzymatic sensors and provides a promising way to develop a new efficient nonenzymatic electrochemical sensor. Supporting Information Supporting information contains UV-Vis spectra, IR spectra, TGA curve, XPS spectra for V 2p core levels, SEM image, EDS spectra, UV-Vis spectra, Tauc’s plot, BET isothermal plot, effect of pH on the electrocatalytic activity, effect of concentration of VS2 NPs , cyclic voltammorams of synthesized VS2 NPs,operating potential vs relative amperometric response plot, anti-interference ability test and long term stability test of VS2/Nf/GCE.


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

Acknowledgements Authors are thankful to Prof. A. Mondal, Department of Chemistry, IIEST, India, for helping necessary corrections. A. Sarkar is indebted to UGC (BSR), India, for her SRF [File. No. F.7223/2009(BSR)]. The authors acknowledge DST-project (Scheme No. SB/S1/IC-33/2013) for funding and also MHRD (India) for providing instrumental facilities to the Department of Chemistry, IIEST, Shibpur. References (1) Nossol, E.; Zarbin, A. J. G. A Simple and Innovative Route to Prepare a Novel Carbon nanotube/prussian Blue Electrode and its Utilization as a Highly Sensitive H2O2 Amperometric Sensor. Adv. Funct. Mater. 2009, 19, 3980−3986. (2) Yoo, S. K.; Starnes, T. W.; Deng, Q.; Huttenlocher, A. Lyn is a Redox Sensor that Mediates Leukocyte Wound Attraction in Vivo. Nature 2011, 480, 109−112. (3) Tsiafoulis, C. G.; Trikalitis, P. N.; Prodromidis, M. I. Synthesis, Characterization and Performance of Vanadium Hexacyanoferrate as Electrocatalyst of H2O2. Elecrtochem. Commun. 2005, 7, 1380–1384. (4) Keen, O.S.; Baik, S.; Linden, K. G.; Aga, D. S.; Love, N. G. Enhanced Biodegradation of Carbamazepine after UV/H2O2 Advanced Oxidation. Environ. Sci. Technol. 2012, 46, 6222−6227. (5) Usui, Y.; Sato, K.; Tanaka, M. Catalytic Dihydroxylation of Olefins with Hydrogen Peroxide: An Organic-Solvent- and Metal-free System. Chem. Int. Ed. 2003, 42, 5623–5625. (6) Wei, Y.; Zhang, Yi.; Liu, Z.; Guo, M. A Novel Profluorescent Probe for Detecting Oxidative Stress Induced by Metal and H2O2 in Living Cells. Chem. Commun. 2010, 46, 4472–4474. (7) Pramanik, D.; Dey, S. G. Active Site Environment of Heme-bound Amyloid Peptide Associated with Alzheimer’s Disease. J. Am. Chem. Soc. 2011, 133, 81–87. (8) Dickinson, B. C.; Chang, C. J. A Targetable Fluorescent Probe for Imaging Hydrogen Peroxide in the Mitochondria of Living Cells. J. Am. Chem. Soc. 2008, 130, 9638–9639.



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Graphical Abstract

Solvothermal TETA 220 oC [VO(acda)2 ]

VS2 NPs


Newly Designed Amperometric Biosensor for Hydrogen Peroxide and

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