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1.
The authors describe the fabrication of an interconnected edge-exposed graphene nanostructure via chemical vapor deposition (CVD) of foliated graphene onto a network of alumina nanofibers. The fibers such obtained are shown to enable ultra-sensitive voltammetric determination of dopamine (DA), uric acid (UA) and ascorbic acid (AA). The electrode displays powerful and persistent electro oxidative behavior and excellent electron transport properties. Cyclic voltammetry and differential pulse voltammetry demonstrate excellent selectively and sensitivity for AA, DA and UA, with typical peaks at ?0.08 V, +0.19 V, and +0.34 V (vs. SCE), respectively. Under optimum conditions, the calibration plots are linear in the 1–80 μM range for DA, in the 1–60 μM range for UA, and in the 0.5–60 μM range for UA, with detection limits of 0.47 μM, 0.28 μM and 0.59 μM, respectively. The sensor was successfully applied to the simultaneous determination of DA and UA in the presence of AA in spiked urine sample.
Graphical abstract Material with high density of graphene foliates grown over highly aligned nano-dimensional ceramic fibers is used as electrode for simultaneous highly sensitive electrochemical determination of DA in the presence of UA and AA with a considerably low limit of detection.
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2.
We describe a chemical exfoliation method for the preparation of MoS2 nanosheets. The nanosheets were incorporated into poly(3,4-ethylenedioxythiophene) (PEDOT) by electrodeposition on a glassy carbon electrode (GCE) to form a nanocomposite. The modified GCE is shown to enable simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA). Due to the synergistic effect of MoS2 and PEDOT, this electrode displays better properties in terms of electrocatalytic oxidation of AA, DA and UA than pure PEDOT, which is illustrated by cyclic voltammetry and differential pulse voltammetry (DPV). Under optimum conditions and at pH 7.4, the respective sensitivities and best working potentials are as follows: AA: 1.20 A?mM?1?m?2, 30 mV; DA: 36.40 A?mM?1?m?2, 210 mV; UA: 105.17 A?mM?1?m?2, 350 mV. The calculated detection limits for AA, DA and UA are 5.83 μM, 0.52 μM and 0.95 μM, respectively. The modified electrode was applied to the detection of the three species in human urine samples and gave satisfactory results.
Graphical abstract MoS2 nanosheets were prepared by a facile chemical exfoliation method. MoS2 and poly(3,4-ethylenedioxythiophene) nanocomposite modified glassy carbon electrodes were fabricated, which are shown to enable simultaneous determination of ascorbic acid, dopamine and uric acid with high sensitivity and selectivity.
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3.
We describe the modification of a carbon paste electrode (CPE) with multiwalled carbon nanotubes (MWCNT) and an ionic liquid (IL). Electrochemical studies revealed an optimized composition of 60 % graphite, 20 % paraffin, 10 % MWCNT and 10 % IL. In a next step, the optimized CPE was modified with palladium nanoparticles (Pd-NPs) by applying a double-pulse electrochemical technique. The resulting electrode was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, cyclic voltammetry, and electrochemical impedance spectroscopy. It gives three sharp and well separated oxidation peaks for ascorbic acid (AA), dopamine (DA), and uric acid (UA), with peak separations of 180 and 200 mV for AA-DA and DA-UA, respectively. The sensor enables simultaneous determination of AA, DA and UA with linear responses from 0.6 to 112, 0.1 to 151, and 0.5 to 225 μM, respectively, and with 200, 30 and 150 nM detection limits (at an S/N of 3). The method was successfully applied to the determination of AA, DA, and UA in spiked samples of human serum and urine. Figure
The CPE was modified with multiwalled carbon nanotubes and an ionic liquid. After optimization the electrode was further modified with palladium nanoparticles. The resulting electrode gives three sharp and well separated oxidation peaks for ascorbic acid, dopamine and uric acid  相似文献   

4.
Mei  He  Sheng  Qu  Wu  Huimin  Zhang  Xiuhua  Wang  Shengfu  Xia  Qinghua 《Mikrochimica acta》2015,182(15):2395-2401

Alloy nanoparticles of the type PtxFe (where x is 1, 2 or 3) were synthesized by coreduction with sodium borohydride in the presence of carbon acting as a chemical support. The resulting nanocomposites were characterized by scanning electron microscopy and X-ray diffraction. The nanocomposite was placed on a glassy carbon electrode, and electrochemical measurements indicated an excellent catalytic activity for the oxidation of glucose even a near-neutral pH values and at a working voltage as low as 50 mV (vs. SCE). Under optimized conditions, the sensor responds to glucose in the 10.0 μM to 18.9 mM concentration range and with a 3.0 μM detection limit (at an S/N ratio of 3). Interferences by ascorbic acid, uric acid, fructose, acetamidophenol and chloride ions are negligible.

Nonenzymatic sensing of glucose is demonstrated at neutral pH values and low working potential using a glassy carbon electrode modified with platinum-iron alloy nanoparticles on a carbon support.

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5.

Single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT) and graphene have been tested as carbon allotropes for the modification of carbon screen-printed electrodes (CSPEs) to simultaneously determine melatonin (MT) and serotonin (5-HT). Two groups of CSPEs, both 4 mm in diameter, were explored: The first includes commercial SWCNT, MWCNT and graphene, the second includes SWCNT, MWCNT, graphene oxide nanoribbons and reduced nanoribbons that were drop casted on the electrodes. The carbon nanomaterials enhanced the electroactive area in the following order: CSPE

Carbon nanomaterials on screen-printed electrodes: smart electrochemistry for fast, simultaneous and reliable detection of serotonin the molecule of happiness and melatonin the molecule of darkness.

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6.
Xu  Wailan  He  Junlin  Gao  Liuliu  Zhang  Jing  Yu  Chao 《Mikrochimica acta》2015,182(13):2115-2122

We describe a nanostructured immunosensor for the cardiovascular biomarker netrin 1. A glassy carbon electrode was consecutively modified with multi-walled carbon nanotubes (MWCNTs), nafion (to retain the MWCNTs), thionine-coated gold nanoparticles (Thi@AuNPs), and monoclonal antibodies against netrin 1. The modified electrode was characterized by transmission electron microscopy, cyclic voltammetry, differential pulse voltammetry, UV-visible spectrophotometry and X-ray diffraction. The presence of Thi@AuNPs warrants direct and convenient immobilization of the antibody. This immunoelectrode enables netrin 1 to be determined, best at a voltage of −300 mV (vs. SCE), with a limit of detection of 30 fg mL−1 (at an S/N ratio of 3) after a 50 min incubation time. The detection range extends from 0.09 to 1800 pg∙mL−1. The method is simple, sensitive, specific and reproducible. We presume this stable and reproducible biosensor to be useful for the early detection of cardiovascular diseases.

A high sensitivity immunoassay was developed for the detection of netrin 1 based on multi-walled carbon nanotubes, thionine and gold nanoparticles. Its excellent performance is ascribed to the good conductivity of MWCNTs and the combination of materials.

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7.
Cui  Haochen  Wu  Jayne  Eda  Shigetoshi  Chen  Jiangang  Chen  Wei  Zheng  Lei 《Mikrochimica acta》2015,182(13):2361-2367

A label-free and single-step method is reported for rapid and highly sensitive detection of bisphenol A (BPA) in aqueous samples. It utilizes an aptamer acting as a probe molecule immobilized on a commercially available array of interdigitated aluminum microelectrodes. BPA was quantified by measuring the interfacial capacitance change rate caused by the specific binding between bisphenol A and the immobilized aptamer. The AC signal also induces an AC electrokinetic effect to generate microfluidic motion for enhanced binding. The capacitive aptasensor achieves a limit of detection as low as 10 fM(2.8 fg ⋅ mL − 1) with a 20 s response time. The method is inexpensive, highly sensitive, rapid and therefore provides a promising technology for on-site detection of BPA in food and water samples.

A. AC electrokinetics effect plays a vital role in BPA detection by introducing microfluidic movement to accelerate the molecular transport to the electrode surface.

B. The ACEK capacitive aptasensor has a limit of detection as low as 10 fM (2.8 fg ⋅ mL − 1) with a 20-s response time.

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8.
Sun  Dong  Xu  Caiqun  Long  Jianghua  Ge  Teng 《Mikrochimica acta》2015,182(15):2601-2606

This article describes an electrochemical sensor for the dye additive Sunset Yellow (SY). It consists of a carbon paste electrode modified with nanostructured resorcinol-formaldehyde (RF) resin. The RF resin warrants strong signal enhancement and a strongly increased oxidation peak currents of SY at 0.66 V (vs. SCE). The effects of pH value, amount of RF polymer, accumulation potential and time were optimized. The sensor has a linear response to SY in the 0.3 to 125 nM concentration range, and the limit of detection is 0.09 nM after a 2-min accumulation time. The electrode was applied to the analysis of samples of wastewater and drinks, and the results are consistent with those obtained by HPLC.

Nanostructured resorcinol-formaldehyde (RF) resin was prepared and used as a material for electrochemical determination of Sunset Yellow.

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9.
Bhaisare  Mukesh Lavkush  Talib  Abou  Khan  M. Shahnawaz  Pandey  Sunil  Wu  Hui-Fen 《Mikrochimica acta》2015,182(13):2173-2181

A jelly-like form of carbon dots (C-dots) was prepared by microwave-assisted synthesis from citric acid in the presence of tetraoctylammonium bromide. The effect of the concentration of tetraoctylammonium bromide was examined. The synthesized carbon dots were characterized by UV–vis, XRD, FTIR, fluorescence and HR-TEM. Fluorescence extends from 350 to 600 nm, and the corresponding excitation wavelengths range from 300 to 460 nm. Quantum yields are at around 0.11. A cytotoxicity study showed carbon dots to be cell permeable and biocompatible which renders them appropriate for imaging applications. The dots were used to image HeLa cell lines via the blue fluorescence of the dots.

C-dots were synthesized from citric acid by microwave heating in presence of varying concentrations of tetraoctylammonium bromide (TOAB) as a micellar template. The excellent optical properties of the nanoparticles make them well suitable for bio-imaging of HeLa cells.

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10.

We have studied the direct electrochemistry of glucose oxidase (GOx) immobilized on electrochemically fabricated graphite nanosheets (GNs) and zinc oxide nanoparticles (ZnO) that were deposited on a screen printed carbon electrode (SPCE). The GNs/ZnO composite was characterized by using scanning electron microscopy and elemental analysis. The GOx immobilized on the modified electrode shows a well-defined redox couple at a formal potential of −0.4 V. The enhanced direct electrochemistry of GOx (compared to electrodes without ZnO or without GNs) indicates a fast electron transfer at this kind of electrode, with a heterogeneous electron transfer rate constant (Ks) of 3.75 s−1. The fast electron transfer is attributed to the high conductivity and large edge plane defects of GNs and good conductivity of ZnO-NPs. The modified electrode displays a linear response to glucose in concentrations from 0.3 to 4.5 mM, and the sensitivity is 30.07 μA mM−1 cm−2. The sensor exhibits a high selectivity, good repeatability and reproducibility, and long term stability.

Graphical representation for the fabrication of GNs/ZnO composite modified SPCE and the immobilization of GOx

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11.
A voltammetric sensor is presented for the simultaneous determination of dopamine (DA) and uric acid (UA) in the presence of ascorbic acid (AA). It is based on a gold electrode (GE) modified with carboxyl-functionalized graphene (CFG) and silver nanocube functionalized DA nanospheres (AgNC@PDA-NS). The AgNC@PDA-NS nanocomposite was characterized by scanning electron microscopy and UV-Vis spectroscopy. The electrochemical behavior of the modified electrode was evaluated by electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. The modified electrode displays good electrocatalytic activity towards DA (typically at 0.14 V vs. Ag/AgCl) and UA (typically at 0.29 V vs. Ag/AgCl) even in the presence of ascorbic acid. Response to DA is linear in the concentration range of 2.5 to 130 μM with a detection limit of 0.25 μM. Response to UA is linear in the concentration range of 10 to 130 μM with a detection limit of 1.9 μM. In addition, the sensitivity for DA and UA is 0.538 and 0.156 μA μM?1 cm?2, respectively. The modified electrode also displays good stability, selectivity and reproducibility.
Graphical abstract The gold electrode modified with polydopamine nanospheres functionalized with silver nanocube and carboxylated graphene is used for simultaneous determination of DA and UA in the presence of AA, with wide linear range and low detection limit.
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12.
A voltammetric sensor for both the individual and the simultaneous determination of ascorbic acid (AA), uric acid (UA) and folic acid (FA) is described. It is based on a glassy carbon electrode (GCE) that was modified with bentonite (Bnt) that was first functionalized with cysteine (Cys) to which gold nanoparticles were linked. The resulting material (referred to as Au-Cys-Bnt) and the other materials were characterized by UV-vis spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray analysis and electrochemical methods. The XRD peak positions of bentonite and Cys-functionalized bentonite prove the incorporation of Cys into bentonite. The XPS spectrum of Au-Cys-Bnt confirms the interaction of gold nanoparticles with the thiol group of Cys. The modified GCE displays high electrocatalytic activity for the oxidation of AA, UA and FA, typically at 0.19, 0.41, and 0.73 V (vs. SCE), respectively. Differential pulse voltammetric data show a linear response that covers the 1 μM to 25 mM concentration range for AA, the 1 to 200 μM concentration range for UA, and two linear ranges for FA, one from 5 to 100 μM and one from 100 μM to 1.5 mM. The sensor was applied to the determination of AA, UA and FA in (spiked) multi-vitamin syrup, bird serum and milk samples.
Graphical abstract Schematic of a sensor for simultaneous and individual electrochemical determination of ascorbic, uric, and folic acids in real samples. The sensor consists of a glassy carbon electrode that was modified with a nanocomposite prepared from bentonite that was first functionalized with cysteine to which gold nanoparticles were linked.
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13.
A glassy carbon electrode (GCE) was anodically oxidized by cyclic voltammetry (CV) in 0.05 M sulfuric acid to introduce hydroxy groups on its surface (GCEox). Next, an imidazolium alkoxysilane (ImAS) is covalently tethered to the surface of the GCEox via silane chemistry. This electrode is further modified with graphene oxide (GO) which, dispersed in water, spontaneously assembles on the electrode surface through electrostatic interaction and π-interaction to give an electrode of type GO/ImAS/GCE. Electroreduction of GO and GCEox by CV yields electroreduced GO (erGO) and an electrode of the type erGO/ImAS/GCE. This electrode displays excellent electrocatalytic activity for the oxidation of ascorbic acid (AA), dopamine (DA) and uric acid (UA). Three fully resolved anodic peaks (at ?50 mV, 150 mV and 280 mV vs. Ag/AgCl) are observed during differential pulse voltammetry (DPV). Under optimized conditions, the linear detection ranges are from 30 to 2000 μM for AA, from 20 to 490 μM for UA, and from 0.1 to 5 μM and from 5 μM to 200 μM (two linear ranges) for DA. The respective limits of detection (for an S/N of 3) are 10 μM, 5 μM and 0.03 μM. The GCE modified with erGO and ImAS performs better than a bare GCE or a GCE modified with ImAS only, and also outperforms many other reported electrodes for the three analytes. The method was successfully applied to simultaneous analysis of AA, DA and UA in spiked human urine.
Graphical abstract Differential pulse voltammetric simultaneous determination of ascorbic acid, dopamine and uric acid is achieved on a glassy carbon electrode modified with electroreduced graphene oxide and imidazolium groups, through anodic treatment of glassy carbon and silane chemistry.
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14.
Zheng  Dongyun  Liu  Xiaojun  Zhu  Shanying  Cao  Huimin  Chen  Yaguang  Hu  Shengshui 《Mikrochimica acta》2015,182(15):2403-2410

We describe an electrochemical sensor for nitric oxide that was obtained by modifying the surface of a nanofiber carbon paste microelectrode with a film composed of hexadecyl trimethylammonium bromide and nafion. The modified microelectrode displays excellent catalytic activity in the electrochemical oxidation of nitric oxide. The mechanism was studied by scanning electron microscopy and cyclic voltammetry. Under optimal conditions, the oxidation peak current at a working voltage of 0.75 V (vs. SCE) is related to the concentration of nitric oxide in the 2 nM to 0.2 mM range, and the detection limit is as low as 2 nM (at an S/N ratio of 3). The sensor was successfully applied to the determination of nitric oxide released from mouse hepatocytes.

NO electrochemical sensor based on CTAB-Nafion/CNFPME was fabricated through a simple method and applied to detect NO released from mouse hepatocytes successfully.

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15.
Wang  Yong  Qu  Jianhang  Li  Shufang  Dong  Ying  Qu  Jianying 《Mikrochimica acta》2015,182(13):2277-2283

We describe an electrochemical sensor for simultaneous determination of hydroquinone (HQ) and catechol (CC). A glassy carbon electrode (GCE) was modified with gold nanoparticles, L-cysteine, and ZnS/NiS@ZnS quantum dots using a layer-by-layer technique. The materials were characterized by X-ray diffractometry, field emission scanning electron microscopy, and electrochemical impedance and Fourier transform infrared spectroscopy. Cyclic voltammetry and differential pulse voltammetry revealed this modified GCE to represent a highly sensitive sensor for the simultaneous determination of HQ and CC. The anodic peak current for HQ at a working voltage of 80 mV (vs. Ag/AgCl) is related to its concentration in the 0.1 to 300 μM range (even in the presence of 0.1 mM of CC). The anodic peak current for CC at a working voltage of 184 mV is related to its concentration in the 0.5 to 400 μM range (even in the presence of 0.1 mM of HQ). The detection limits (at an S/N ratio of 3) are 24 and 71 nM for HQ and CC, respectively. The modified GCE was successfully applied to the determination of HQ and CC in aqueous solutions and gave satisfactory results.

A glassy carbon electrode was modified with gold nanoparticles, ZnS/NiS@ZnS quantum dots and L-cysteine and used for simultaneous determination of hydroquinone and catechol.

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16.
Ju  Ke-Jian  Feng  Jin-Xia  Feng  Jiu-Ju  Zhang  Qian-Li  Xu  Tian-Qi  Wei  Jie  Wang  Ai-Jun 《Mikrochimica acta》2015,182(15):2427-2434

A nanocomposite consisting of coral-like gold nanostructures on reduced graphene oxide (RGO) was synthesized with the assistance of dimethylbiguanide (DMBG). It was then fabricated on a glassy carbon electrode, coating with cysteamine in order to enable the immobilization of acetylcholinesterase (AChE) as a model enzyme whose activity of hydrolyzing the substrate of acetylthiocholine is inhibited by the pesticide triazophos. The biosensor has response to acetylthiocholine in the 0.3 ~ 300 μM concentration range at 0.65 V (vs. SCE). The inhibition of the enzyme by triazophos can be determined in concentrations of up to 210 ppb, with a detection limit of 0.35 ppb of triazophos (S/N = 3). The biosensor is highly reproducible and acceptably stable.

Coral-like gold nanostructures supported on reduced graphene oxide were synthesized with the assistance of dimethylbiguanide to fabricate an acetylcholinesterase (AChE) biosensor, which exhibited high reproducibility and good stability, providing a good platform for the detection of organophosphorus pesticides.

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17.
Yang  Tao  Chen  Huaiyin  Yang  Ruirui  Jiang  Yuhang  Li  Weihua  Jiao  Kui 《Mikrochimica acta》2015,182(15):2623-2628

Thin-layered molybdenum disulfide (MoS2) was intercalated, via ultrasonic exfoliation, into self-doped polyaniline (SPAN). This material, when placed on a glassy carbon electrode (GCE), exhibits excellent electrical conductivity and synergistic catalytic activity with respect to the detection of bisphenol A (BPA). The electrochemical response of the modified GCE to BPA was investigated by cyclic voltammetry and differential pulse voltammetry. Under optimal conditions, the oxidation peak current (measured best at 446 mV vs. SCE) is related to the concentration of BPA in the range from 1.0 nM to 1.0 μM, and the detection limit is 0.6 nM.

Thin-layered molybdenum disulfide (MoS2) was intercalated into self-doped polyaniline (SPAN) via ultrasonic exfoliation. The special conjugated structure and functional groups of MoS2-SPAN composite help to adsorb BPA easily. MoS2-SPAN has a synergistic effect for catalyzing the oxidation of BPA. The BPA electrochemical sensor based on MoS2-SPAN has a high sensitivity and low detection limit.

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18.
The authors describe a voltammetric sensor for simultaneous determination of dopamine (DA), uric acid (UA), L-tyrosine (Tyr), and the diuretic drug hydrochlorothiazide (HCTZ). The assay is based on the use of graphene nanowalls deposited on a tantalum substrate. The nanowalls are characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, electrochemical impedance spectroscopy, and cyclic voltammetry. The nanowalls are vertically grown on the substrate by direct-current arc plasma jet chemical vapor deposition. The modified electrode is shown to enable simultaneous differential pulse voltammetric determination of DA, UA, Tyr, and HCTZ. The graphene nanowalls display a large specific surface, high conductivity, and a large number of catalytically active sites for oxidation of analytes. Simultaneous detection is performed best at a pH value of 7.0 and at peak potentials of 0.124 V (vs. SCE) for DA, 0.256 V for UA, 0.536 V for Tyr and 0.708 V for HCTZ. The respective detection limits are 0.04 μM, 0.1 μM, 0.6 μM and 0.4 μM. The results show that this graphene wall modified electrode is a promising tool for the design of sensitive, selective, and stable sensors.
Graphical abstract The graphene-based differential pulse voltammetric sensor for simultaneous determination of dopamine, uric acid, L-tyrosine, and hydrochlorothiazide exhibits high selectivity, sensitivity, and stability.
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19.

A nanocomposite consisting of reduced graphene oxide decorated with palladium-copper oxide nanoparticles (Pd-CuO/rGO) was synthesized by single-step chemical reduction. The morphology and crystal structure of the nanocomposite were characterized by field-emission scanning electron microscopy, high resolution transmission electron microscopy and X-ray diffraction analysis. A 3-electrode system was fabricated by screen printing technology and the Pd-CuO/rGO nanocomposite was dropcast on the carbon working electrode. The catalytic activity towards glucose in 0.2 M NaOH solutions was analyzed by linear sweep voltammetry and amperometry. The steady state current obtained at a constant potential of +0.6 V (vs. Ag/AgCl) showed the modified electrode to possess a wide analytical range (6 μM to 22 mM), a rather low limit of detection (30 nM), excellent sensitivity (3355 μA∙mM−1∙cm−2) and good selectivity over commonly interfering species and other sugars including fructose, sucrose and lactose. The sensor was successfully employed to the determination of glucose in blood serum.

A highly sensitive nonenzymatic electrochemical sensor was fabricated using a Pd-CuO composite with reduced graphene oxide. The sensor has a wide detection range and was used to sense glucose in blood serum

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20.
Zhao  Li  Wu  Genghuang  Cai  Zhixiong  Zhao  Tingting  Yao  Qiuhong  Chen  Xi 《Mikrochimica acta》2015,182(11):2055-2060

We describe an anodic stripping voltammetric (ASV) method for glucose sensing that widely expands the typical amperometric i-t response of glucose sensors. The electrode is based on a working electrode consisting of a glassy carbon electrode modified with Pt-Pd nanoparticles (NPs; in an atomic ratio of 3:1) on a reduced graphene oxide (rGO) support. The material was prepared via the spontaneous redox reaction between rGO, PdCl4 2− and PtCl4 2− without any additional reductant or surfactant. Unlike known Pt-based sensors, the use of Pt3Pd NPs results in an ultrasensitive ASV approach for sensing glucose even at near-neutral pH values. If operated at a working voltage as low as 0.06 V (vs. SCE), the modified electrode can detect glucose in the 2 nM to 300 μM concentration range. The lowest detectable concentration is 2 nM which is much lower than the LODs obtained with other amperometric i-t type sensing approaches, most of which have LODs at a μM level. The sensor is not interfered by the presence of 0.1 M of NaCl.

We describe an anodic stripping voltammetric method for glucose sensing that widely expands the typical amperometric i-t response of glucose sensors (2 nM to 300 μM). The electrode is based on a glassy carbon electrode modified with Pt-Pd nanoparticles on a reduced graphene oxide (rGO) support.

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