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1.
We report a simple approach to the production of carbon fiber‐based amperometric microbiosensors for selective detection of hydrogen peroxide (H2O2), which was achieved by electrometallization of carbon fiber microelectrodes (CFMs) by electrodeposition of Pt nanoparticles. The Pt‐carbon hybrid sensing interface provided a sensitivity of 7711±587 μA ? mM?1 ? cm?2, a detection limit of 0.53±0.16 μM (S/N=3), a linear range of 0.8 μM–8.6 mM, and a response time of <2 sec. The morphologies of the Pt nanoparticle‐modified CFMs were characterized by scanning electron microscopy. To achieve selectivity, permseletive layers, polyphenylenediamine (PPD) and Nafion, were deposited resulting in exclusion of the anionic and cationic interferents, ascorbic acid and dopamine, respectively, at their physiologically relevant concentrations. The resultant sensors displayed a sensitivity to hydrogen peroxide of 1381±72 μA ? mM?1 ? cm?2, and a detection limit of 0.86±0.19 μM (S/N=3). This simple and rapid metallization method converts carbon fiber microelectrodes, which are readily accessible, to microscale Pt electrodes in 2 min, providing a platform for oxidase‐based amperometric biosensors with improved spatial resolution over more commonly used platinum electrode array microprobes.  相似文献   

2.
The electrochemical behavior of ferrocene has been studied in a number of room temperature ionic liquids. Diffusion‐controlled, well‐defined anodic and cathodic peaks were found for the Fc/Fc+ (ferrocene/ferrocenium) oxidation/reduction on the gold electrode. Ohmic resistance R between working and auxiliary electrodes was deduced from impedance measurements. Cyclic voltammograms were corrected for the base line current as well as for the ohmic drop (IR). The formal potential 1/2(Epa+Epc) for ferrocene reduction/oxidation in aprotic ionic liquids tested is within a relatively narrow range and may be approximated by the value of 0.527±0.018 V (against the cryptate Ag/Ag+222 in acetonitrile reference). Ferrocene diffusion coefficients, calculated from the peak current dependence on the sweep rate, were of the order of 10?7 cm2 s?1.  相似文献   

3.
In this study, a novel non‐enzymatic hydrogen peroxide (H2O2) sensor was fabricated based on gold nanoparticles/carbon nanotube/self‐doped polyaniline (AuNPs/CNTs/SPAN) hollow spheres modified glassy carbon electrode (GCE). SPAN was in‐site polymerized on the surface of SiO2 template, then AuNPs and CNTs were decorated by electrostatic absorption via poly(diallyldimethylammonium chloride). After the SiO2 cores were removed, hollow AuNPs/CNTs/SPAN spheres were obtained and characterized by transmission electron microscopy (TEM), field‐emission scanning electron microscopy (FESEM) and Fourier transform infrared spectroscopy (FTIR). The electrochemical catalytic performance of the hollow AuNPs/CNTs/SPAN/GCE for H2O2 detection was evaluated by cyclic voltammetry (CV) and chronoamperometry. Using chronoamperometric method at a constant potential of ?0.1 V (vs. SCE), the H2O2 sensor displays two linear ranges: one from 5 µM to 0.225 mM with a sensitivity of 499.82 µA mM?1 cm?2; another from 0.225 mM to 8.825 mM with a sensitivity of 152.29 µA mM?1 cm?2. The detection limit was estimated as 0.4 µM (signal‐to‐noise ratio of 3). The hollow AuNPs/CNTs/SPAN/GCE also demonstrated excellent stability and selectivity against interferences from other electroactive species. The sensor was further applied to determine H2O2 in disinfectant real samples.  相似文献   

4.
Poly(hydroxyethylmethacrylate)‐based hydrogel membranes were applied to microfabricated, microdisk electrode arrays (MDEAs) of 50 μm (5184 disks), 100 μm (1296 disks) and 250 μm (207 disks) (d/r=4; A= 0.1 cm2) and studied by cyclic voltammetry (CV) in 1.0 mM ferrocene monocarboxylic acid (FcCO2H). The membrane produced an order of magnitude decrease in current densities and a shift to quasi reversibility due to a decrease in the Dappt of FcCO2H, from 4.51×10?6 cm2 s?1 to 1.42×10?8 cm2 s?1, (2.18×10?8 cm2 s?1 from release experiments). The MDEA050 (comprising 50 μm disks) maintained its enhanced current density attributes confirming its value as an effective electrode for biosensors. Finite element modeling (FEM) simulations successfully replicated the voltammograms of the MDEAs.  相似文献   

5.
A conductometric system with a multipumping module and a gas-diffusion cell has been developed to determine free and total sulfur dioxide (SO2) in wine. The developed method has two protocols to determine both types of SO2 using the same system. For free SO2, sulfite is converted to H2SO4 by acidification and diffusion with H2O2 in an acceptor channel. The sample was previously hydrolyzed by mixing the sample with NaOH and heated at 70?°C prior making the determination of total SO2 in order to break the bonds of the combined SO2. Free and total SO2 were determined in the ranges of 2.5–25.4 and 10.2–76.2?mg L?1 with a sample throughput of 13 and 12?h?1, respectively. The calibration curves of free and total SO2 were in the range of ΔG (mS cm?1)?=?(–1.0242?±?0.2871)?+?(0.6613?±?0.0201) [SO2, mg L?1], r2 of 0.997 and ΔG (mS cm?1)?=?(–0.5850?±?0.1678)?+?(0.1236?±?0.0033) [SO2, mg L?1], r2 of 0.997. The proposed automated method is simple and easy to apply for the determination of SO2 in wine using simple reagents.  相似文献   

6.
The reactions of S + OH → SO + H (1) and SO + OH → SO2 + H (2) were studied in a discharge flow reactor coupled to an EPR spectrometer. The rate constants obtained under the pseudo-first-order conditions with an excess of S or SO were found to be k1 = (6.6 ± 1.4) × 10?11 and k2 = (8.4 ± 1.5) × 10?11 at room temperature. Units are cm3/molec·sec. Besides no reactivity was observed between S and CO2 at 298 K and between CIO and SO2 up to 711 K.  相似文献   

7.
A novel enzyme‐free glucose sensor was proposed by preparation of nanorods decorated nanopore arrays (NRs/NPAs) on 316L stainless steel simply by electrochemical treatments. The NRs/NPAs sensor displays two linear ranges towards glucose determination, one range from 1 μM to 1.2 mM with a sensitivity of 202.2 μA ? cm?2 ? mM?1, another range from 1.2 mM to 7.7 mM with a sensitivity of 59.18 μA?cm?2 ? mM?1. The detection limit is 0.5 μM. The NRs/NPAs electrode exhibits excellent stability, good selectivity and reproducibility, rendering it suitable for glucose monitoring.  相似文献   

8.
Summary: Anthracene sulfonic acid doped polyaniline nanomaterials were prepared through the chemical oxidative polymerisation process. Ammonium peroxydisulfate (APS) was employed as oxidant. Scanning electron microscopy (SEM) results show the resultant polyaniline (PANi) materials exhibited nanofibrillar morphology with diameter sizes less than 300 nm. Using the nanofibrillar PANI, amperometric biosensors for H2O2 and erythromycin were constructed through the drop-coating technique. Anthracene sulfonic acid (ASA) doped PANi and the test enzymes horseradish peroxidase, (HRP), or cytochrome P450 3A4, (CYP4503A4) were mixed in phosphate buffer solution before drop coating onto the electrode. The resultant biosensors displayed typical Michaelis-Menten behaviour. The apparent Michaelis-Menten constant obtained was 0.18 ± 0.01 mM and 0.80 ± 0.02 µM L−1 for the peroxide and erythromycin biosensor respectively. The sensitivity for the peroxide sensor was 3.3 × 10−3 A · cm−2 · mM−1, and the detection limit was found to be 1.2 × 10−2 mM respectively. Similarly, the sensitivity for the erythromycin sensor was in the same order at 1.57 × 10−3 A · cm−2 · mM−1 and detection limit was found to be 7.58 × 10−2 µM.  相似文献   

9.
The direct electron transfer of glucose oxidase (GOx) was achieved based on the immobilization of CdSe@CdS quantum dots on glassy carbon electrode by multi-wall carbon nanotubes (MWNTs)-chitosan (Chit) film. The immobilized GOx displayed a pair of well-defined and reversible redox peaks with a formal potential (E θ’) of ?0.459 V (versus Ag/AgCl) in 0.1 M pH 7.0 phosphate buffer solution. The apparent heterogeneous electron transfer rate constants (k s) of GOx confined in MWNTs-Chit/CdSe@CdS membrane were evaluated as 1.56 s?1 according to Laviron's equation. The surface concentration (Γ*) of the electroactive GOx in the MWNTs-Chit film was estimated to be (6.52?±?0.01)?×?10?11?mol?cm?2. Meanwhile, the catalytic ability of GOx toward the oxidation of glucose was studied. Its apparent Michaelis–Menten constant for glucose was 0.46?±?0.01 mM, showing a good affinity. The linear range for glucose determination was from 1.6?×?10?4 to 5.6?×?10?3?M with a relatively high sensitivity of 31.13?±?0.02 μA?mM?1?cm?2 and a detection limit of 2.5?×?10?5?M (S/N=3).  相似文献   

10.
Adsorption of carbon dioxide on H‐ZSM‐5 zeolite (Si:Al=11.5:1) was studied by means of variable‐temperature FT‐IR spectroscopy, in the temperature range of 310–365 K. The adsorbed CO2 molecules interact with the zeolite Brønsted‐acid OH groups bringing about a characteristic red‐shift of the O? H stretching band from 3610 cm?1 to 3480 cm?1. Simultaneously, the ν3 mode of adsorbed CO2 is observed at 2345 cm?1. From the variation of integrated intensity of the IR absorption bands at both 3610 and 2345 cm?1, upon changing temperature (and CO2 equilibrium pressure), the standard adsorption enthalpy of CO2 on H‐ZSM‐5 is ΔH0=?31.2(±1) kJ mol?1 and the corresponding entropy change is ΔS0=?140(±10) J mol?1 K?1. These results are discussed in the context of available data for carbon dioxide adsorption on other protonic, and also alkali‐metal exchanged, zeolites.  相似文献   

11.
A nonenzymatic glucose sensor was successfully established by electrochemically decorating cobalt oxides (CoOx) on a nanoporous gold electrode (NPG) using cobalt hexacyanoferrate (CoHCF) as a precursor. It exhibited high sensitivity and long‐term stability as well as satisfactory quantification of glucose concentration in human serum samples. The morphology and surface analysis of the resulting CoOx/NPG were carefully characterized. Two detection methods, cyclic voltammetry and amperometry, were employed to evaluate the performance of CoOx/NPG towards glucose sensing in alkaline solution. Using cyclic voltammetry, at ?0.5 V, the glucose partial oxidation peak current is linear to the glucose concentration up to 14 mM with a sensitivity of 283.7 µA mM?1 cm?2. A linear amperometric response at 0.55 V was obtained in the glucose concentration range from 2 µM to 2 mM with a sensitivity of 2025 µA mM?1 cm?2 and a response time <3 s.  相似文献   

12.
The catalytic properties of peroxidase basic isoenzymes (PBI's) from Brassica napus towards trans‐resveratrol (t‐Res) oxidation were demonstrated by the first time by conventional UV‐visible spectroscopic measurements. The enzymatic reaction rate was studied under different experimental conditions and the kinetics parameters were determined. An amperometric biosensor based on Brassica napus PBI's to determine t‐Res is also proposed by the first time. The method employs a dialysis membrane covered, PBI's entrapped and ferrocene (Fc)‐embedded carbon paste electrode (PBI's‐Fc‐CP) and is based on the fact that the decreased amount of H2O2 produced by the action of PBI's is proportional to the oxidised amount of t‐Res in the solution. Comparative amperometric experiments showed that, in spite of PBI's activity was much lower than commercial horseradish peroxidase (HRP) activity, t‐Res was a much better substrate for PBI's biosensors than those biosensors constructed by using HRP. The PBI's‐Fc‐CP biosensors showed a very good stability during at least twenty days. The reproducibility and the repeatability were 4.5% and 8.3%, respectively, showing a good biosensor performance. The calibration curve was linear in the t‐Res concentration (ct‐Res) range from 1×10?6 to 2.5×10?5 M, with a sensibility of (2.31±0.05)×106 nA M?1. The lowest ct‐Res value measured experimentally for a signal to noise ratio of 3 : 1 was 0.83 μM.  相似文献   

13.
The aim of this work was to demonstrate that various types of nanostructures provide different gains in terms of sensitivity or detection limit albeit providing the same gain in terms of increased area. Commercial screen printed electrodes (SPEs) were functionalized with 100 µg of bismuth oxide nanoparticles (Bi2O3 NPs), 13.5 µg of gold nanoparticles (Au NPs), and 4.8 µg of multi-wall carbon nanotubes (MWCNTs) to sense hydrogen peroxide (H2O2). The amount of nanomaterials to deposit was calculated using specific surface area (SSA) in order to equalize the additional electroactive surface area. Cyclic voltammetry (CV) experiments revealed oxidation peaks of Bi2O3 NPs, Au NPs, and MWCNTs based electrodes at (790 ± 1) mV, (386 ± 1) mV, and (589 ± 1) mV, respectively, and sensitivities evaluated by chronoamperometry (CA) were (74 ± 12) µA mM?1 cm?2, (129 ± 15) ±A mM?1 cm?2, and (54 ± 2) ±A mM?1 cm?2, respectively. Electrodes functionalized with Au NPs showed better sensing performance and lower redox potential (oxidative peak position) compared with the other two types of nanostructured SPEs. Interestingly, the average size of the tested Au NPs was 4 nm, under the limit of 10 nm where the quantum effects are dominant. The limit of detection (LOD) was (11.1 ± 2.8) ±M, (8.0 ± 2.4) ±M, and (3.4 ± 0.1) ±M for Bi2O3 NPs, Au NPs, and for MWCNTs based electrodes, respectively.  相似文献   

14.
At present, a highly sensitive hydrogen peroxide (H2O2) sensor is fabricated by ferrocene based naphthaquinone derivatives as 2,3‐Diferrocenyl‐1,4‐naphthoquinone and 2‐bromo‐3‐ferrocenyl‐1,4‐naphthoquinone. These ferrocene based naphthaquinone derivatives are characterized by H‐NMR and C‐NMR. The electrochemical properties of these ferrocene based naphthaquinone are investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) on modified glassy carbon electrode (GCE). The modified electrode with ferrocene based naphthaquinone derivatives exhibits an improved voltammetric response to the H2O2 redox reaction. 2‐bromo‐3‐ferrocenyl‐1,4‐naphthoquinone show excellent non‐enzymatic sensing ability towards H2O2 response with a detection limitation of 2.7 μmol/L a wide detection range from 10 μM to 400 μM in H2O2 detection. The sensor also exhibits short response time (1 s) and good sensitivity of 71.4 μA mM?1 cm?2 and stability. Furthermore, the DPV method exhibited very high sensitivity (18999 μA mM?1 cm?2) and low detection limit (0.66 μM) compared to the CA method. Ferrocene based naphthaquinone derivative based sensors have a lower cost and high stability. Thus, this novel non‐enzyme sensor has potential application in H2O2 detection.  相似文献   

15.
Rate coefficients and/or mechanistic information are provided for the reaction of Cl‐atoms with a number of unsaturated species, including isoprene, methacrolein ( MACR ), methyl vinyl ketone ( MVK ), 1,3‐butadiene, trans‐2‐butene, and 1‐butene. The following Cl‐atom rate coefficients were obtained at 298 K near 1 atm total pressure: k(isoprene) = (4.3 ± 0.6) × 10?10cm3 molecule?1 s?1 (independent of pressure from 6.2 to 760 Torr); k( MVK ) = (2.2 ± 0.3) × 10?10 cm3 molecule?1 s?1; k( MACR ) = (2.4 ± 0.3) × 10?10 cm3 molecule?1 s?1; k(trans‐2‐butene) = (4.0 ± 0.5) × 10?10 cm3 molecule?1 s?1; k(1‐butene) = (3.0 ± 0.4) × 10?10 cm3 molecule?1 s?1. Products observed in the Cl‐atom‐initiated oxidation of the unsaturated species at 298 K in 1 atm air are as follows (with % molar yields in parentheses): CH2O (9.5 ± 1.0%), HCOCl (5.1 ± 0.7%), and 1‐chloro‐3‐methyl‐3‐buten‐2‐one (CMBO, not quantified) from isoprene; chloroacetaldehyde (75 ± 8%), CO2 (58 ± 5%), CH2O (47 ± 7%), CH3OH (8%), HCOCl (7 ± 1%), and peracetic acid (6%) from MVK ; CO (52 ± 4%), chloroacetone (42 ± 5%), CO2 (23 ± 2%), CH2O (18 ± 2%), and HCOCl (5%) from MACR ; CH2O (7 ± 1%), HCOCl (3%), acrolein (≈3%), and 4‐chlorocrotonaldehyde (CCA, not quantified) from 1,3‐butadiene; CH3CHO (22 ± 3%), CO2 (13 ± 2%), 3‐chloro‐2‐butanone (13 ± 4%), CH2O (7.6 ± 1.1%), and CH3OH (1.8 ± 0.6%) from trans‐2‐butene; and chloroacetaldehyde (20 ± 3%), CH2O (7 ± 1%), CO2 (4 ± 1%), and HCOCl (4 ± 1%) from 1‐butene. Product yields from both trans‐2‐butene and 1‐butene were found to be O2‐dependent. In the case of trans‐2‐butene, the observed O2‐dependence is the result of a competition between unimolecular decomposition of the CH3CH(Cl)? CH(O?)? CH3 radical and its reaction with O2, with kdecomp/kO2 = (1.6 ± 0.4) × 1019 molecule cm?3. The activation energy for decomposition is estimated at 11.5 ± 1.5 kcal mol?1. The variation of the product yields with O2 in the case of 1‐butene results from similar competitive reaction pathways for the two β‐chlorobutoxy radicals involved in the oxidation, ClCH2CH(O?)CH2CH3 and ?OCH2CHClCH2CH3. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 334–353, 2003  相似文献   

16.
A cheap amperometric and optical sensor for glucose, based on an ITO electrode coated with electrodeposited Co/Al hydrotalcite (HT) is described. Cobalt based HT shows a reversible electrochromic behavior which can be exploited for the development of an optical sensor. Working in the optical mode, the linearity range of the sensor is between 0.008 and 0.13 mM with a sensitivity of 1.14 mM?1?cm?2, whereas when working in the amperometric mode, the linearity ranges from 0.002 to 1.5 mM with a sensitivity of 4.24×10?4 A?mM?1?cm?2. The sensor has been successfully employed for the determination of glucose in a serum sample.  相似文献   

17.
An extensive study of the surface chemical changes to poly(ether sulphone) (PES) ultrafiltration membranes is made for the first time by the use of time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) after photoirradiation at 254 nm with irradiances varying from 10 to 300 mJ cm?2 in a nitrogen atmosphere. Complementary information is provided by analysis with x‐ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR). The versatility, superior specificity and sensitivity of using ToF‐SIMS to investigate degradation phenomena are highlighted. The combined results demonstrate that photoirradiation causes a number of chemical changes to the surface: incorporation of oxygen; degradation of the benzene rings and formation of oxidized carbon species; depletion of carbon; reduction of ? SO2? to some extent; formation of ? OH, C?O and ? SO3H groups; and probable formation of ? C6H4? O? C6H5 end‐groups. In addition, no ? OSO3H groups are formed and no formation of SO2 is detected. Also, it is shown that chain scission dominates below an irradiation dose of ~200 mJ cm?2 (at 254 nm in a nitrogen atmosphere). At higher doses, cross‐linking becomes dominant. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

18.
The electrochemical redox properties of a surface‐confined thin solid film of nanostructured cobalt(II) tetracarboxyphthalocyanine integrated with multiwalled carbon nanotube (nanoCoTCPc/MWCNT) have been investigated. This novel nanoCoTCPc/MWCNT material was characterized using SEM, TEM, zeta analysis and electrochemical methods. The nanoCoTCPc/MWCNT nanohybrid material exhibited an extra‐ordinarily high conductivity (15 mS cm?1), which is more than an order of magnitude greater than that of the MWCNT‐SO3H (527 µS cm?1) and three orders of a magnitude greater than the nanoCoTCPc (4.33 µS cm?1). The heterogeneous electron transfer rate constant decreases as follows: nanoCoTCPc/MWCNT (kapp≈19.73×10?3 cm s?1)>MWCNT‐SO3H (kapp≈11.63×10?3 cm s?1)>nanoCoTCPc (kapp≈1.09×10?3 cm s?1). The energy‐storage capability was typical of pseudocapacitive behaviour; at a current density of 10 µA cm?2, the pseudocapacitance decreases as nanoCoTCPc/MWCNT (3.71×10?4 F cm?2)>nanoCoTCPc (2.57×10?4 F cm?2)>MWCNT‐SO3H (2.28×10?4 F cm?2). The new nanoCoTCPc/MWCNT nanohybrid material promises to serve as a potential material for the fabrication of thin film electrocatalysts or energy‐storage devices.  相似文献   

19.
Glutathione (GSH) tagged with a ferrocene (Fc) label at its C‐terminal was synthesized via coupling ferrocenyl amine to glutathione using o‐(benzotriazol‐1‐yl)‐N,N,N′,N′‐tetramethyluronium (HBTU)/1‐hydroxybenzotrizole (HOBt). The presence of Fc yielded well defined voltammetric signals, rendering the Fc‐tagged GSH (GSH‐Fc) suitable for electrochemical studies of GSH binding to other biological species. The interaction of GSH‐Fc with bovine serum albumin (BSA) was investigated, and a binding ratio of 1.41±0.06 (GSH‐Fc/BSA) and an affinity constant Ka of 6.53±2.01×106 M?1 were determined. These results compare well with those measured by fluorescence using untagged GSH, suggesting that the attachment of Fc to GSH does not significantly perturb the GSH structure and binding behavior. By contrasting the binding behavior to several compounds that are known to conjugate to different domains of BSA, the voltammetric study confirmed that GSH‐Fc binds at subdomain IIA of BSA with high affinity. The versatility of GSH‐Fc for studying GSH binding to surface‐confined proteins was also demonstrated with the GSH binding to electroinactive Zn‐metallothionein (Zn7‐MT) through hydrogen binding at the region between the Zn7‐MT α and β domains.  相似文献   

20.
The ferrocene/NaY zeolite composites (Fc/NaY) are introduced on the surface of a glassy carbon electrode together with the hydrophobic ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF6). The modified electrode thus constructed exhibits a pair of reversible redox peaks corresponding to ferrocene. Additionally the peak separation remains almost constant (58–75 mV) and the value of the ratio ipa/ipc is close to 1 for scan rates in the range from 10 to 1000 mV s?1. The effects of the scan rate, aqueous supporting electrolytes, hydrophobic ionic liquid and the contents of ferrocene encapsulated by electrochemistry are investigated. The extrazeolite electron transfer process is discussed. Furthermore, the Fc/NaY/IL‐modified electrode shows good mediation towards oxidation of ascorbic acid, dopamine, hydroquinone, and catechol.  相似文献   

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