Direct electrochemistry of glucose oxidase and biosensing for glucose based on boron-doped carbon nanotubes modified electrode.

PubMed

Deng, Chunyan; Chen, Jinhua; Chen, Xiaoli; Xiao, Chunhui; Nie, Lihua; Yao, Shouzhuo

2008-03-14

Due to their unique physicochemical properties, doped carbon nanotubes are now extremely attractive and important nanomaterials in bioanalytical applications. In this work, selecting glucose oxidase (GOD) as a model enzyme, we investigated the direct electrochemistry of GOD based on the B-doped carbon nanotubes/glassy carbon (BCNTs/GC) electrode with cyclic voltammetry. A pair of well-defined, quasi-reversible redox peaks of the immobilized GOD was observed at the BCNTs based enzyme electrode in 0.1M phosphate buffer solution (pH 6.98) by direct electron transfer between the protein and the electrode. As a new platform in glucose analysis, the new glucose biosensor based on the BCNTs/GC electrode has a sensitivity of 111.57 microA mM(-1)cm(-2), a linear range from 0.05 to 0.3mM and a detection limit of 0.01mM (S/N=3). Furthermore, the BCNTs modified electrode exhibits good stability and excellent anti-interferent ability to the commonly co-existed uric acid and ascorbic acid. These indicate that boron-doped carbon nanotubes are the good candidate material for the direct electrochemistry of the redox-active enzyme and the construction of the related enzyme biosensors.

An electrochemiluminescent biosensor for glucose based on the electrochemiluminescence of luminol on the nafion/glucose oxidase/poly(nickel(II)tetrasulfophthalocyanine)/multi-walled carbon nanotubes modified electrode.

PubMed

Qiu, Bin; Lin, Zhenyu; Wang, Jian; Chen, Zhihuang; Chen, Jinhua; Chen, Guonan

2009-04-15

A poly(nickel(II) tetrasulfophthalocyanine)/multi-walled carbon nanotubes composite modified electrode (polyNiTSPc/MWNTs) was fabricated by electropolymerization of NiTSPc on MWNTs-modified glassy carbon electrode (GCE). The modified electrode was found to be able to greatly improve the emission of luminol electrochemiluminescence (ECL) in a solution containing hydrogen peroxide. Glucose oxidase (GOD) was immobilized on the surface of polyNiTSPc/MWNTs modified GC electrode by Nafion to establish an ECL glucose sensor. Under the optimum conditions, the linear response range of glucose was 1.0x10(-6) to 1.0x10(-4) mol L(-1) with a detection limit of 8.0x10(-8) mol L(-1) (defined as the concentration that could be detected at the signal-to-noise ratio of 3). The ECL sensor showed an outstanding well reproducibility and long-term stability. The established method has been applied to determine the glucose concentrations in real serum samples with satisfactory results.

Fabrication of high performance bioanode based on fruitful association of dendrimer and carbon nanotube used for design O2/glucose membrane-less biofuel cell with improved bilirubine oxidase biocathode.

PubMed

Korani, Aazam; Salimi, Abdollah

2013-12-15

In this study, the preparation of an integrated modified electrode based on the covalent attachment of glucose dehydrogenase (GDH) enzyme and safranin O to amine-derivative multiwalled carbon nanotubes (MWCNTs-NH2) modified glassy carbon (GC) electrode using G2.5-carboxylated PAMAM dendrimer (Den) as linking agent is reported. The obtained results indicated that the proposed system has effective bioelectrocatalytic activity toward glucose oxidation at 100 mV with onset potential of -130 mV (vs. Ag/AgCl). The performance of the prepared hybrid system of GC/MWCNTs-NH2/Den/GDH/Safranin as anode in a membraneless enzyme-based glucose/O2 biofuel cell is further evaluated. The biocathode in this system was composed of bilirubin oxidase (BOX) enzyme immobilized onto a bilirubin modified carbon nanotube GC electrode. Immobilized BOX onto CNTs/bilirubin not only show direct electron transfer but also it has excellent electrocatalytic activity toward oxygen reduction at a positive potential of 610 mV. The open circuit voltage of the cell was 590 mV. The maximum current density was 0.5 mA cm(-2), while maximum power density of 108 μW cm(-2) was achieved at voltage of 330 mV. The immobilized enzymes in anode and cathode are very stable and output power of the BFC is approximately constant after 12 h continues operation. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids.

PubMed

Mehdi, B Layla; Rutkowska, Iwona A; Kulesza, Pawel J; Cox, James A

2013-06-01

Modification of electrodes with nm-scale organically modified silica films with pores diameters controlled at 10- and 50-nm is described. An oxidation catalyst, mixed-valence ruthenium oxide with cyano crosslinks or gold nanoparticles protected by dirhodium-substituted phosophomolybdate (AuNP-Rh 2 PMo 11 ), was immobilized in the pores. These systems comprise size-exclusion films at which the biological compounds, phosphatidylcholine and cardiolipin, were electrocatalytically oxidized without interference from surface-active concomitants such as bovine serum albumin. 10-nm pores were obtained by adding generation-4 poly(amidoamine) dendrimer, G4-PAMAM, to a (CH 3 ) 3 SiOCH 3 sol. 50-nm pores were obtained by modifying a glassy carbon electrode (GC) with a sub-monolayer film of aminopropyltriethoxylsilane, attaching 50-nm diameter poly(styrene sulfonate), PSS, spheres to the protonated amine, transferring this electrode to a (CH 3 ) 3 SiOCH 3 sol, and electrochemically generating hydronium at uncoated GC sites, which catalyzed ormosil growth around the PSS. Voltammetry of Fe(CN) 6 3- and Ru(NH 3 ) 6 3+ demonstrated the absence of residual charge after removal of the templating agents. With the 50-nm system, the pore structure was sufficiently defined to use layer-by-layer electrostatic assembly of AuNP-Rh 2 PMo 11 therein. Flow injection amperometry of phosphatidylcholine and cardiolipin demonstrated analytical utility of these electrodes.

Porous carbon derived from disposable shaddock peel as an excellent catalyst toward VO2+/VO2+ couple for vanadium redox battery

NASA Astrophysics Data System (ADS)

Liu, J.; Wang, Z. A.; Wu, X. W.; Yuan, X. H.; Hu, J. P.; Zhou, Q. M.; Liu, Z. H.; Wu, Y. P.

2015-12-01

Functional porous carbon (PC) derived from bio-friendly shaddock peel has been firstly explored as catalyst for vanadium redox flow battery (VRB). The prepared PC is micro-mesoporous with high BET surface area of 882.7 m2 g-1, has some surface oxygen-containing functional groups, and is doped with N and P heteroatoms. These three factors greatly favor the electrochemical reactions of VO2+/VO2+ on the PC modified glass carbon (PC-GC). Compared with the naked GC and graphite modified GC, the PC-GC presents a lower peak separation (66 mV), higher anodic current density (17.1 mA cm-2) and cathodic current density (15.0 mA cm-2). The VRB using PC modified graphite felt (GF) as positive electrode demonstrates an enhanced voltage efficiency of 82.7% at the current density of 60 mA cm-2, and a better rate performance than that from the virginal GF.

Spontaneous grafting: a novel approach to graft diazonium cations on gold nanoparticles in aqueous medium and their self-assembly on electrodes.

PubMed

Kesavan, Srinivasan; John, S Abraham

2014-08-15

The spontaneous grafting of aminophenyl groups on gold nanoparticles (AuNPs) by reaction with in situ generated 4-aminophenyl diazonium cations (APD) in an aqueous medium was described. The spontaneous grafting was likely to proceed by transfer of electrons from AuNPs to the APD cations to form an aminophenyl radical and subsequent attachment with AuNPs. The aminophenyl (AP) functionalized gold nanoparticles (AP-AuNPs) were characterized by UV-visible spectroscopy, high resolution-transmission electron microscopy (HR-TEM), X-ray diffraction, FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and surface-enhanced Raman spectroscopy (SERS). The absence of characteristic vibrational bands corresponding to diazonium group in the FT-IR spectrum confirmed the reduction of the aminophenyl diazonium cations at the surface of AuNPs. The spontaneous attachment of AP on AuNPs was confirmed by XPS from the observed binding energy values for -NH2 at 399.4 eV and -N=N- at 400.2 eV. The SERS spectrum reveals the presence Au-C (437 cm(-1)) bond on AP-AuNPs. Further, the AP-AuNPs were self-assembled on GC/ITO electrode (AP-AuNPs modified electrode) with the aid of free amine groups present on the surface of AP-AuNPs via Michael's nucleophilic addition reaction. The AP-AuNPs modified electrode was characterized by cyclic voltammetry, impedance spectroscopy, UV-visible spectroscopy and scanning electron microscopy. Impedance studies show that the electron transfer reaction of [Fe(CN)6](3-/4-) was higher at the AP-AuNPs modified electrode (1.81×10(-4) cm s(-1)) than at bare (3.77×10(-5) cm s(-1)) GC electrode. Finally, the electrocatalytic activity of the AP-AuNPs modified electrode was demonstrated by studying the oxidation of dopamine (DA). Copyright © 2014 Elsevier Inc. All rights reserved.

A facile one-pot preparation of Co3O4/g-C3N4 heterojunctions with excellent electrocatalytic activity for the detection of environmental phenolic hormones

NASA Astrophysics Data System (ADS)

Sun, Yanjuan; Jiang, Jizhou; Liu, Yi; Wu, Shengli; Zou, Jing

2018-02-01

The Co3O4/g-C3N4 heterojunctions were prepared by a facile one-pot thermal decomposition technique. Compared with g-C3N4, it was found that Co3O4/g-C3N4 heterojunctions possessed a higher Brunner-Emmet-Teller (BET) surface area, which was beneficial to the diffusion of aim molecules on the electrode surfaces. And the optimal Co3O4/g-C3N4 heterojunctions exhibited a narrower band gap and a higher donor density, resulting in an excellent electrocatalytic activity for environmental phenolic hormones. Moreover, the Co3O4/g-C3N4 heterojunctions were used for the electrochemical sensing of environmental phenolic hormones such as bisphenol A, pentachlorophenol, p-nitrophenol and octylphenol. All detection ranges reached three orders of magnitude, showing a lower limit of detection of 10-9 mol L-1. So, sensitivity and accurate determination of environmental phenolic hormones in real water samples may use this Co3O4/g-C3N4 heterojunctions modified electrode.

Continuous monitoring of L-glutamate released from cultured nerve cells by an online sensor coupled with micro-capillary sampling.

PubMed

Niwa, O; Horiuchi, T; Torimitsu, K

1997-01-01

A small volume L-glutamate online sensor was developed in order to monitor changes in the local concentration of L-glutamate released from cultured nerve cells. Syringe pump in the suction mode is used to sample extracellular fluid continuously from a glass micro-capillary and the concentration of L-glutamate can be determined by using a glassy carbon (GC) electrode modified with an Os-polyvinylpyridine mediator bottom film containing horseradish peroxidase and a bovine serum albumin top layer containing L-glutamate oxidase. The overall efficiency of L-glutamate detection with a sensor is 71% under optimum conditions due to an efficient enzymatic reaction at the modified electrode in the thin layer radial flow cell. As a result, we achieved a detection limit of 7-15 nM and a linear range of 50 nM to 10 microM. In an in vitro experiment, the extracellular fluid near a particular nerve cell can be sampled with this micro-pipet and continuously introduced into the modified GC electrode in the radial flow cell via suction provided by a syringe pump. The nerve cells are stimulated by the KCl in a glass capillary and the L-glutamate concentration change can be monitored by changing the distance between the sampling pipet and the nerve cells.

Monolithic quasi-solid-state dye-sensitized solar cells based on graphene modified mesoscopic carbon counter electrodes

NASA Astrophysics Data System (ADS)

Rong, Yaoguang; Li, Xiong; Liu, Guanghui; Wang, Heng; Ku, Zhiliang; Xu, Mi; Liu, Linfeng; Hu, Min; Yang, Ying; Han, Hongwei

2013-03-01

We have developed a monolithic quasi-solid-state dye-sensitized solar cell (DSSC) based on graphene modified mesoscopic carbon counter electrode (GC-CE), which offers a promising prospect for commercial applications. Based on the design of a triple layer structure, the TiO2 working electrode layer, ZrO2 spacer layer and carbon counter electrode (CE) layer are constructed on a single conducting glass substrate by screen-printing. The quasi-solid-state polymer gel electrolyte employs a polymer composite as the gelator and could effectively infiltrate into the porous layers. Fabricated with normal carbon counter electrode (NC-CE) containing graphite and carbon black, the device shows a power conversion efficiency (PCE) of 5.09% with the fill factor (FF) of 0.63 at 100 mW cm-2 AM1.5 illumination. When the NC-CE is modified with graphene sheets, the PCE and FF could be enhanced to 6.27% and 0.71, respectively. This improvement indicates excellent conductivity and high electrocatalytic activity of the graphene sheets, which have been considered as a promising platinum-free electrode material for DSSCs.

Simple flow injection for determination of sulfite by amperometric detection using glassy carbon electrode modified with carbon nanotubes-PDDA-gold nanoparticles.

PubMed

Amatatongchai, Maliwan; Sroysee, Wongduan; Chairam, Sanoe; Nacapricha, Duangjai

2015-02-01

A new approach is presented for sensitive and selective measurement of sulfite (SO3(2-)) in beverages based on a simple flow injection system with amperometric detection. In this work, the sulfite sensor was a glassy carbon electrode modified with multiwall carbon nanotubes-poly(diallyldimethylammonium chloride)-gold nanoparticles composites (CNTs-PDDA-AuNPs/GC). Electrochemical oxidation of sulfite with this electrode was first studied in 0.1M phosphate buffer (pH 7.0) using cyclic voltammetry. The results indicated that the CNTs-PDDA-AuNPs/GC electrode possesses electrocatalytic activity for the oxidation of sulfite with high sensitivity and selectivity. Sulfite was quantified using amperometric measurement with the new sensor at +0.4V vs Ag/AgCl in conjunction with flow injection. The linear working range for the quantitation of sulfite was 2-200 mg L(-1) (r(2)=0.998) with a detection limit of 0.03 mg L(-1) (3σ of blank) and an estimated precision of 1.5%.The proposed method was successfully applied to the determination of sulfite in fruit juices and wines with a sample throughput of 23 samples per hour. Copyright © 2014 Elsevier B.V. All rights reserved.

The simultaneous electrochemical detection of ascorbic acid, dopamine, and uric acid using graphene/size-selected Pt nanocomposites.

PubMed

Sun, Chia-Liang; Lee, Hsin-Hsien; Yang, Jen-Ming; Wu, Ching-Chou

2011-04-15

In this study, a graphene/Pt-modified glassy carbon (GC) electrode was created to simultaneously characterize ascorbic acid (AA), dopamine (DA), and uric acid (UA) levels via cyclic voltammetry (CV) and differential pulse voltammetry (DPV). During the preparation of the nanocomposite, size-selected Pt nanoparticles with a mean diameter of 1.7 nm were self-assembled onto the graphene surface. In the simultaneous detection of the three aforementioned analytes using CV, the electrochemical potential differences among the three detected peaks were 185 mV (AA to DA), 144 mV (DA to UA), and 329 mV (AA and UA), respectively. In comparison to the CV results of bare GC and graphene-modified GC electrodes, the large electrochemical potential difference that is achieved via the use of the graphene/Pt nanocomposites is essential to the distinguishing of these three analytes. An optimized adsorption of size-selected Pt colloidal nanoparticles onto the graphene surface results in a graphene/Pt nanocomposite that can provide a good platform for the routine analysis of AA, DA, and UA. Copyright © 2011 Elsevier B.V. All rights reserved.

EDTA assisted synthesis of hydroxyapatite nanoparticles for electrochemical sensing of uric acid.

PubMed

Kanchana, P; Sekar, C

2014-09-01

Hydroxyapatite nanoparticles have been synthesized using EDTA as organic modifier by a simple microwave irradiation method and its application for the selective determination of uric acid (UA) has been demonstrated. Electrochemical behavior of uric acid at HA nanoparticle modified glassy carbon electrode (E-HA/GCE) has been investigated by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), linear sweep voltammetry (LSV) and amperometry. The E-HA modified electrode exhibits efficient electrochemical activity towards uric acid sensing without requiring enzyme or electron mediator. Amperometry studies revealed that the fabricated electrode has excellent sensitivity for uric acid with the lowest detection limit of 142 nM over a wide concentration range from 1 × 10(-7) to 3 × 10(-5)M. Moreover, the studied E-HA modified GC electrode exhibits a good reproducibility and long-term stability and an admirable selectivity towards the determination of UA even in the presence of potential interferents. The analytical performance of this sensor was evaluated for the detection of uric acid in human urine and blood serum samples. Copyright © 2014. Published by Elsevier B.V.

DNA/nickel oxide nanoparticles/osmium(III)-complex modified electrode toward selective oxidation of l-cysteine and simultaneous detection of l-cysteine and homocysteine.

PubMed

Sharifi, Ensiyeh; Salimi, Abdollah; Shams, Esmaeil

2012-08-01

The modification of glassy carbon (GC) electrode with electrodeposited nickel oxide nanoparticles (NiOxNPs) and deoxyribonucleic acid (DNA) is utilized as a new efficient platform for entrapment of osmium (III) complex. Surface morphology and electrochemical properties of the prepared nanocomposite modified electrode (GC/DNA/NiOxNPs/Os(III)-complex) were investigated by FESEM, cyclic voltammetry and electrochemical impedance spectroscopy techniques. Cyclic voltammetric results indicated the excellent electrocatalytic activity of the resulting electrode toward oxidation of l-cysteine (CySH) at reduced overpotential (0.1 V vs. Ag/AgCl). Using chronoamperometry to CySH detection, the sensitivity and detection limit of the biosensor are obtained as 44 μA mM(-1) and 0.07 μM with a concentration range up to 1000 μM. The electrocatalytic activity of the modified electrode not only for oxidation of low molecular-mass biothiols derivatives such as, glutathione, l-cystine, l-methionine and electroactive biological species ( dopamine, uric acid, glucose) is negligible but also for very similar biothiol compound (homocysteine) no recognizable response is observed at the applied potential window. Furthermore, the simultaneous voltammetric determination of l-cysteine and homocysteine compounds without any separation or pretreatment process was reported for the first time in this work. Finally, the applicability of sensor for the analysis of CySH concentration in complex serum samples was successfully demonstrated. Highly selectivity, excellent electrocatalytic activity and stability, remarkable antifouling property toward thiols and their oxidation products, as well as the ability for simultaneous detection of l-cysteine and homocysteine are remarkably advantageous of the proposed DNA based biosensor. Copyright © 2012 Elsevier B.V. All rights reserved.

Direct electrochemistry of hemoglobin immobilized in CuO nanowire bundles.

PubMed

Li, Yueming; Zhang, Qian; Li, Jinghong

2010-11-15

It is one of main challenges to find the suitable materials to enhance the direct electron transfer between the electrode and redox protein for direct electrochemistry field. Nano-structured metal oxides have attracted considerable interest because of unique properties, well biocompatibility, and good stability. In this paper, the copper oxide nanowire bundles (CuO NWBs) were prepared via a template route, and the bioelectrochemical performances of hemoglobin (Hb) on the CuO NWBs modified glass carbon electrodes (denoted as Hb-CuO NWBs/GC) were studied. TEM and XRD were used to characterize the morphology and structure of the as synthesized CuO NWBs. Fourier transform-infrared spectroscopy (FT-IR) proved that Hb in the CuO NWBs matrix could retain its native secondary structure. A pair of well-defined and quasi-reversible redox peaks at approximately -0.325 V (vs. Ag/AgCl saturated KCl) were shown in the cyclic voltammogram curve for the Hb-CuO NWBs/GC electrode, which indicated the direct electrochemical behavior. The Hb-CuO NWBs/GC electrode also displayed a good electrocatalytic activity toward the reduction of hydrogen peroxide. These results indicate that the CuO NWBs are good substrates for immobilization of biomolecules and might be promising in the fields of (bio) electrochemical analysis. Copyright © 2010 Elsevier B.V. All rights reserved.

Carbohydrate and alditol analysis by high-performance anion-exchange chromatography coupled with electrochemical detection at a cobalt-modified electrode.

PubMed

Casella, Innocenzo G; Contursi, Michela

2003-07-01

A cobalt oxyhydroxide film dispersed on a carbon electrode surface was characterized and proposed as an amperometric sensor for determination of alditols and carbohydrates in flowing streams. Complex mixtures of carbohydrates were separated by anion-exchange chromatography using a moderately alkaline solution as mobile phase. The cobalt modified electrode (GC-Co) was employed under a constant applied potential of 0.5 V (vs Ag/AgCl). Under these experimental conditions the detection limits (S/N=3) for all analyzed electroactive molecules ranged between 0.3 micromol L(-1) and 1.5 micromol L(-1) and the dynamic linear ranges spanned generally three orders of magnitude above the relevant detection limits. Analytical determinations of carbohydrates and alditols in red and white wines, are reported.

A Novel of Multi-wall Carbon Nanotubes/Chitosan Electrochemical Sensor for Determination of Cupric ion

NASA Astrophysics Data System (ADS)

Tan, Funeng; Li, Lei

2018-03-01

A multi-wall carbon nanotubes/Chitosan electrochemical sensor had been fabricated by dropping CHS/MWNT solution directly onto the GC surface. The sensor was charactered by cyclic voltammetry and AC impedance with K3Fe(CN)6 as a electrochemical probe; Cyclic voltammograms(CV) and electrochemical impedance spectroscopy(EIS) indicated that the active area and electrochemical behavior of the sensor increased and improved significantly after the electrode was modified by carbon nanotubes dispersed by the chitosan. The sensor showed good electrocatalytic activity of K3Fe(CN)6. Also, from the cyclic voltammograms, we can see the process was diffusion controlled on the bare electrode and kinetics and diffusion controlled on the modified electrode. Finally Cu2+ responsed sensitively at the sensor which supplied a new method for the detection of Cu2+.

A label-free photoelectrochemical biosensor for urokinase-type plasminogen activator detection based on a g-C3N4/CdS nanocomposite.

PubMed

Liu, Xing-Pei; Chen, Jing-Shuai; Mao, Chang-Jie; Niu, He-Lin; Song, Ji-Ming; Jin, Bao-Kang

2018-09-26

Herein, we established a novel ultrasensitive photoelectrochemical biosensor for detecting urokinase-type plasminogen activator (u-PA), based on a g-C 3 N 4 /CdS nanocomposite. The prepared nanocomposite was characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible absorption spectroscopy, and Fourier transform infrared spectroscopy, thus indicating that the nanocomposite was prepared successfully. In the typical process, the prepared nanocomposite was deposited on the surface of a bare FTO electrode. After being air-dried, the g-C 3 N 4 /CdS nanocomposite modified electrode was successively incubated with antibody against urokinase-type plasminogen activator and the blocking agent BSA to produce a photoelectrochemical biosensor for u-PA. In the presence of target u-PA antigen, the photocurrent response of the prepared biosensor electrode decreased significantly. The proposed novel photoelectrochemical biosensor exhibited good sensitivity, specificity, and reproducibility for u-PA detection, and a low detection limit of 33 fg mL -1 , ranging from 1 μg mL -1 -0.1 pg mL -1 . The proposed strategy should provide a promising method for detection of other biomarkers. Copyright © 2018 Elsevier B.V. All rights reserved.

Fullerene-C60-modified electrode as a sensitive voltammetric sensor for detection of nandrolone--an anabolic steroid used in doping.

PubMed

Goyal, Rajendra N; Gupta, Vinod K; Bachheti, Neeta

2007-07-30

The electrochemical behaviour of nandrolone is investigated by cyclic, differential pulse and square-wave voltammetry in phosphate buffer system at fullerene-C60-modified electrode. The modified electrode shows an excellent electrocatalytic activity towards the oxidation of nandrolone resulting in a marked lowering in the peak potential and considerable improvement of the peak current as compared to the electrochemical activity at the bare glassy carbon electrode. The oxidation process is shown to be irreversible and diffusion-controlled. A linear range of 50 microM to 0.1 nM is obtained along with a detection limit and sensitivity of 0.42 nM and 0.358 nA nM(-1), respectively, in square-wave voltammetric technique. A diffusion coefficient of 4.13x10(-8) cm2 s(-1) was found for nandrolone using chronoamperometry. The effect of interferents, stability and reproducibility of the proposed method were also studied. The described method was successfully employed for the determination of nandrolone in human serum and urine samples. A cross-validation of observed results by GC-MS indicates that the results are in good agreement with each other.

A highly sensitive electrochemical biosensor for catechol using conducting polymer reduced graphene oxide-metal oxide enzyme modified electrode.

PubMed

Sethuraman, V; Muthuraja, P; Anandha Raj, J; Manisankar, P

2016-10-15

The fabrication, characterization and analytical performances were investigated for a catechol biosensor, based on the PEDOT-rGO-Fe2O3-PPO composite modified glassy carbon (GC) electrode. The graphene oxide (GO) doped conducting polymer poly (3,4-ethylenedioxythiophene) (PEDOT) was prepared through electrochemical polymerization by potential cycling. Reduction of PEDOT-GO was carried out by amperometric method. Fe2O3 nanoparticles were synthesized in ethanol by hydrothermal method. The mixture of Fe2O3, PPO and glutaraldehyde was casted on the PEDOT-rGO electrode. The surface morphology of the modified electrodes was studied by FE-SEM and AFM. Cyclic voltammetric studies of catechol on the enzyme modified electrode revealed higher reduction peak current. Determination of catechol was carried out successfully by Differential Pulse Voltammetry (DPV) technique. The fabricated biosensor investigated shows a maximum current response at pH 6.5. The catechol biosensor exhibited wide sensing linear range from 4×10(-8) to 6.20×10(-5)M, lower detection limit of 7×10(-9)M, current maxima (Imax) of 92.55µA and Michaelis-Menten (Km) constant of 30.48µM. The activation energy (Ea) of enzyme electrode is 35.93KJmol(-1) at 50°C. There is no interference from d-glucose and l-glutamic acid, ascorbic acid and o-nitrophenol. The PEDOT-rGO-Fe2O3-PPO biosensor was stable for at least 75 days when stored in a buffer at about 4°C. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrochemical DNA sensor for anthrax toxin activator gene atxA-detection of PCR amplicons.

PubMed

Das, Ritu; Goel, Ajay K; Sharma, Mukesh K; Upadhyay, Sanjay

2015-12-15

We report the DNA probe functionalized electrochemical genosensor for the detection of Bacillus anthracis, specific towards the regulatory gene atxA. The DNA sensor is fabricated on electrochemically deposited gold nanoparticle on self assembled layer of (3-Mercaptopropyl) trimethoxysilane (MPTS) on GC electrode. DNA hybridization is monitored by differential pulse voltammogram (DPV). The modified GC electrode is characterized by atomic force microscopy (AFM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) method. We also quantified the DNA probe density on electrode surface by the chronocoulometric method. The detection is specific and selective for atxA gene by DNA probe on the electrode surface. No report is available for the detection of B. anthracis by using atxA an anthrax toxin activator gene. In the light of real and complex sample, we have studied the PCR amplicons of 303, 361 and 568 base pairs by using symmetric and asymmetric PCR approaches. The DNA probe of atxA gene efficiently hybridizes with different base pairs of PCR amplicons. The detection limit is found to be 1.0 pM (S/N ratio=3). The results indicate that the DNA sensor is able to detect synthetic target as well as PCR amplicons of different base pairs. Copyright © 2015 Elsevier B.V. All rights reserved.

Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matheu, Roc; Francàs, Laia; Chernev, Petko

Electrochemical reduction of the dizaonium complex, [Ru II(bda)(NO)(N–N 2) 2] 3+, 2 3+ (N–N 2 2+ is 4-(pyridin-4-yl) benzenediazonium and bda 2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid materialmore » has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO 2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO 2, is a very fast and rugged heterogeneous water oxidation catalyst with TOF is of 300 s –1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.« less

Behavior of the Ru-bda water oxidation catalyst covalently anchored on glassy carbon electrodes

DOE PAGES

Matheu, Roc; Francàs, Laia; Chernev, Petko; ...

2015-05-07

Electrochemical reduction of the dizaonium complex, [Ru II(bda)(NO)(N–N 2) 2] 3+, 2 3+ (N–N 2 2+ is 4-(pyridin-4-yl) benzenediazonium and bda 2– is [2,2'-bipyridine]-6,6'-dicarboxylate), in acetone produces the covalent grafting of this molecular complex onto glassy carbon (GC) electrodes. Multiple cycling voltammetric experiments on the GC electrode generates hybrid materials labeled as GC-4, with the corresponding Ru-aqua complex anchored on the graphite surface. GC-4 has been characterized at pH = 7.0 by electrochemical techniques and X-ray absorption spectroscopy (XAS) and has been shown to act as an active catalyst for the oxidation of water to dioxygen. This new hybrid materialmore » has a lower catalytic performance than its counterpart in homogeneous phase and progressively decomposes to form RuO 2 at the electrode surface. The resulting metal oxide attached at the GC electrode surface, GC-RuO 2, is a very fast and rugged heterogeneous water oxidation catalyst with TOF is of 300 s –1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported so far, at neutral pH.« less

2D Hexagonal Boron Nitride (2D-hBN) Explored for the Electrochemical Sensing of Dopamine.

PubMed

Khan, Aamar F; Brownson, Dale A C; Randviir, Edward P; Smith, Graham C; Banks, Craig E

2016-10-04

Crystalline 2D hexagonal boron nitride (2D-hBN) nanosheets are explored as a potential electrocatalyst toward the electroanalytical sensing of dopamine (DA). The 2D-hBN nanosheets are electrically wired via a drop-casting modification process onto a range of commercially available carbon supporting electrodes, including glassy carbon (GC), boron-doped diamond (BDD), and screen-printed graphitic electrodes (SPEs). 2D-hBN has not previously been explored toward the electrochemical detection/electrochemical sensing of DA. We critically evaluate the potential electrocatalytic performance of 2D-hBN modified electrodes, the effect of supporting carbon electrode platforms, and the effect of "mass coverage" (which is commonly neglected in the 2D material literature) toward the detection of DA. The response of 2D-hBN modified electrodes is found to be largely dependent upon the interaction between 2D-hBN and the underlying supporting electrode material. For example, in the case of SPEs, modification with 2D-hBN (324 ng) improves the electrochemical response, decreasing the electrochemical oxidation potential of DA by ∼90 mV compared to an unmodified SPE. Conversely, modification of a GC electrode with 2D-hBN (324 ng) resulted in an increased oxidation potential of DA by ∼80 mV when compared to the unmodified electrode. We explore the underlying mechanisms of the aforementioned examples and infer that electrode surface interactions and roughness factors are critical considerations. 2D-hBN is utilized toward the sensing of DA in the presence of the common interferents ascorbic acid (AA) and uric acid (UA). 2D-hBN is found to be an effective electrocatalyst in the simultaneous detection of DA and UA at both pH 5.0 and 7.4. The peak separations/resolution between DA and UA increases by ∼70 and 50 mV (at pH 5.0 and 7.4, respectively, when utilizing 108 ng of 2D-hBN) compared to unmodified SPEs, with a particularly favorable response evident in pH 5.0, giving rise to a significant increase in the peak current of DA. The limit of detection (3σ) is found to correspond to 0.65 μM for DA in the presence of UA. However, it is not possible to deconvolute the simultaneous detection of DA and AA. The observed electrocatalytic effect at 2D-hBN has not previously been reported in the literature when supported upon carbon or any other electrode. We provide valuable insights into the modifier-substrate interactions of this material, essential for those designing, fabricating, and consequently performing electrochemical experiments utilizing 2D-hBN and related 2D materials.

Fabrication and characterization of electrochemically prepared bioanode (polyaniline/ferritin/glucose oxidase) for biofuel cell application

NASA Astrophysics Data System (ADS)

ul Haque, Sufia; Inamuddin; Nasar, Abu; Asiri, Abdullah M.

2018-01-01

Porous matrix of polyaniline (PANI) has been electrodeposited along with the entrapment of biocompatible redox mediator ferritin (Frt) and glucose oxidase (GOx) on the surface of glassy carbon (GC) electrode. The characterizations have been carried out by X-ray Diffraction (XRD) and Transmission electron microscopy (TEM). The enhanced electrochemical signal transfer rate from enzyme to the electrode surface was due to the intimate contact of the enzyme with the electrochemically polymerized conducting PANI matrix. The PANI/Frt/GOx modified GC bioanode was used to investigate the electrocatalytic activity as a function of the concentration of glucose in the range of 10-60 mM. It was confirmed by the electrochemical impedance spectroscopy (EIS), the thick deposition of PANI layer becomes more compact due to which the charge transfer resistance of PANI matrix becomes higher. All the electrochemical measurements of the electrode were carried out by using cyclic voltammetry (CV) and linear sweep voltammetry (LSV). CV curves were recorded at different scan rates (20-100 mV/s) at 50 mM of glucose in 0.3 M potassium ferrocyanide. A normalized saturation current density of 22.3 ± 2 mA/cm2 was observed for the oxidation of 50 mM glucose at a scan rate of 100 mV/s.

Immobilization of glucose oxidase onto a novel platform based on modified TiO2 and graphene oxide, direct electrochemistry, catalytic and photocatalytic activity.

PubMed

Haghighi, Nasibeh; Hallaj, Rahman; Salimi, Abdollah

2017-04-01

In this work a new organic-inorganic nanocomposite has been introduced for enzyme immobilization. The composite consisting of graphene oxide (GO) and titanium oxide nanoparticles (TiO 2 ) modified with 2, 2'-dithioxo-3, 3'-bis (3-(triethoxysilyl) propyl)-2H, 2'H-[5, 5'-bithiazolylidene]-4, 4'(3H, 3'H)-dione as Organic-Inorganic Supporting Ligand (OISL). The OISL was covalently attached to TiO 2 nanoparticles and employed for obtaining a suitable solid surface to enzyme attachment. The glucose oxidase (GOD) was irreversibly loaded on the GC/GO/TiO 2 -OISL using consecutive cyclic voltammetry. The enzyme immobilization and the enzymatic activity were determined by electrochemical methods. The cyclic voltammogram displayed a pair of well-defined and nearly symmetric redox peaks with a formal potential of -0.465V and an apparent electron transfer rate constant of 1.74s -1 . The GO/TiO 2 -OISL can catalyze the electroreduction and electrooxidation of hydrogen peroxide. The GC/GO/TiO 2 -OISL/GOD electrode was used in the hydrogen peroxide determination. The fabricated nanobiocomposite shows dramatic photoelectrocatalytic activity which evaluated by studying the electrocatalytic activity of the fabricated electrode toward hydrogen peroxide in darkness and in the presences of light. Copyright © 2016 Elsevier B.V. All rights reserved.

Voltammetric pH sensing using carbon electrodes: glassy carbon behaves similarly to EPPG.

PubMed

Lu, Min; Compton, Richard G

2014-09-21

Developing and building on recent work based on a simple sensor for pH determination using unmodified edge plane pyrolytic graphite (EPPG) electrodes, we present a voltammetric method for pH determination using a bare unmodified glassy carbon (GC) electrode. By exploiting the pH sensitive nature of quinones present on carbon edge-plane like sites within the GC, we show how GC electrodes can be used to measure pH. The electro-reduction of surface quinone groups on the glassy carbon electrode was characterised using cyclic voltammetry (CV) and optimised with square-wave voltammetry (SWV) at 298 K and 310 K. At both temperatures, a linear correlation was observed, corresponding to a 2 electron, 2 proton Nernstian response over the aqueous pH range 1.0 to 13.1. As such, unmodified glassy carbon electrodes are seen to be pH dependent, and the Nernstian response suggests its facile use for pH sensing. Given the widespread use of glassy carbon electrodes in electroanalysis, the approach offers a method for the near-simultaneous measurement and monitoring of pH during such analyses.

Highly Stable Glassy Carbon Interfaces for Long-Term Neural Stimulation and Low-Noise Recording of Brain Activity

PubMed Central

Vomero, Maria; Castagnola, Elisa; Ciarpella, Francesca; Maggiolini, Emma; Goshi, Noah; Zucchini, Elena; Carli, Stefano; Fadiga, Luciano; Kassegne, Sam; Ricci, Davide

2017-01-01

We report on the superior electrochemical properties, in-vivo performance and long term stability under electrical stimulation of a new electrode material fabricated from lithographically patterned glassy carbon. For a direct comparison with conventional metal electrodes, similar ultra-flexible, micro-electrocorticography (μ-ECoG) arrays with platinum (Pt) or glassy carbon (GC) electrodes were manufactured. The GC microelectrodes have more than 70% wider electrochemical window and 70% higher CTC (charge transfer capacity) than Pt microelectrodes of similar geometry. Moreover, we demonstrate that the GC microelectrodes can withstand at least 5 million pulses at 0.45 mC/cm2 charge density with less than 7.5% impedance change, while the Pt microelectrodes delaminated after 1 million pulses. Additionally, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) was selectively electrodeposited on both sets of devices to specifically reduce their impedances for smaller diameters (<60 μm). We observed that PEDOT-PSS adhered significantly better to GC than Pt, and allowed drastic reduction of electrode size while maintaining same amount of delivered current. The electrode arrays biocompatibility was demonstrated through in-vitro cell viability experiments, while acute in vivo characterization was performed in rats and showed that GC microelectrode arrays recorded somatosensory evoked potentials (SEP) with an almost twice SNR (signal-to-noise ratio) when compared to the Pt ones. PMID:28084398

Electrochemical determination of dopamine and ascorbic acid at a novel gold nanoparticles distributed poly(4-aminothiophenol) modified electrode.

PubMed

Gopalan, Anantha Iyengar; Lee, Kwang-Pill; Manesh, Kalayil Manian; Santhosh, Padmanabhan; Kim, Jun Heon; Kang, Jae Soo

2007-03-15

A modified electrode is fabricated by embedding gold nanoparticles into a layer of electroactive polymer, poly(4-aminothiophenol) (PAT) on the surface of glassy carbon (GC) electrode. Cyclic voltammetry (CV) is performed to deposit PAT and concomitantly deposit Au nanoparticles. Field emission transmission electron microscopic image of the modified electrode, PAT-Au(nano)-ME, indicates the presence of uniformly distributed Au nanoparticles having the sizes of 8-10nm. Electrochemical behavior of the PAT-Au(nano)-ME towards detection of ascorbic acid (AA) and dopamine (DA) is studied using CV. Electrocatalytic determination of DA in the presence of fixed concentration of AA and vice versa, are studied using differential pulse voltammetry (DPV). PAT-Au(nano)-ME exhibits two well defined anodic peaks at the potential of 75 and 400mV for the oxidation of AA and DA, respectively with a potential difference of 325mV. Further, the simultaneous determination of AA and DA is studied by varying the concentration of AA and DA. PAT-Au(nano)-ME exhibits selectivity and sensitivity for the simultaneous determination of AA and DA without fouling by the oxidation products of AA or DA. PAT and Au nanoparticles provide synergic influence on the accurate electrochemical determination of AA or DA from a mixture having any one of the component (AA or DA) in excess. The practical analytical utilities of the PAT-Au(nano)-ME are demonstrated by the determination of DA and AA in dopamine hydrochloride injection and human blood serum samples.

Self-assembly of a thin highly reduced graphene oxide film and its high electrocatalytic activity

NASA Astrophysics Data System (ADS)

Bai, Yan-Feng; Zhang, Yong-Fang; Zhou, An-Wei; Li, Hai-Wai; Zhang, Yu; Luong, John H. T.; Cui, Hui-Fang

2014-10-01

A thin highly reduced graphene oxide (rGO) film was self-assembled at the dimethyl formamide (DMF)-air interface through evaporation-induced water-assisted thin film formation at the pentane-DMF interface, followed by complete evaporation of pentane. The thin film was transferred onto various solid substrates for film characterization and electrochemical sensing. UV-visible spectrometry, scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemistry techniques were used to characterize the film. An rGO film showing 82.8% of the transmittance at 550 nm corresponds to a few layers of rGO nanosheets. The rGO nanosheets cross-stack with each other, lying approximately in the plane of the film. An rGO film collected on a glassy carbon (GC) electrode exhibited improved electrical conductivity compared to GC, with the electrode charge-transfer resistance (Rct) reduced from 31 Ω to 22 Ω. The as-formed rGO/GC electrode was mechanically very stable, exhibiting significantly enhanced electrocatalytic activity to H2O2 and dopamine. Multiple layers of the rGO films on the GC electrode showed even stronger electrocatalytic activity to dopamine than that of the single rGO film layer. The controllable formation of a stable rGO film on various solid substrates has potential applications for nanoelectronics and sensors/biosensors.

In Situ Laser Activation of Electrochemical Kinetics at Carbon Electrodes

DTIC Science & Technology

1994-05-31

surface reflects the bulk indicate that significant amounts of adsorption occurred f GC structure -o accurately than polished or otherwise these compounds ...value. obtained at the fractured surface for the three painie (6A) and ascorbic add (AA) on fractured GC-20. The compounds are approximately equal while...was significant, but all three compounds exhibited higher r. A not am apparet at the Toir-seal electrodes because the time[ specific mechanism of

Amine oxidase-based biosensors for spermine and spermidine determination.

PubMed

Boffi, Alberto; Favero, Gabriele; Federico, Rodolfo; Macone, Alberto; Antiochia, Riccarda; Tortolini, Cristina; Sanzó, Gabriella; Mazzei, Franco

2015-02-01

The present work describes the development and optimization of electrochemical biosensors for specific determination of the biogenic polyamine spermine (Spm) and spermidine (Spmd) whose assessment represents a novel important analytical tool in food analysis and human diagnostics. These biosensors have been prepared using novel engineered enzymes: polyamine oxidase (PAO) endowed with selectivity towards Spm and Spmd and spermine oxidase (SMO) characterized by strict specificity towards Spm. The current design entails biosensors in which the enzymes were entrapped in poly(vinyl alcohol) bearing styrylpyridinium groups (PVA-SbQ), a photocrosslinkable gel, onto an electrode surface. Screen-printed electrodes (SPEs) were used as electrochemical transducers for enzymatically produced hydrogen peroxide, operating at different potential vs Ag/AgCl according to the material of the working electrode (WE): +700 mV for graphite (GP) or -100 mV for Prussian blue (PB)-modified SPE, respectively. Biosensor performances were evaluated by means of flow injection amperometric (FIA) measurements. The modified electrodes showed good sensitivity, long-term stability and reproducibility. Under optimal conditions, the PAO biosensor showed a linear range 0.003-0.3 mM for Spm and 0.01-0.4 mM for Spmd, while with the SMO biosensor, a linear range of 0.004-0.5 mM for Spm has been obtained. The main kinetic parameters apparent Michaelis constant (K M), turnover number (K cat) and steady-state current (I max) were determined. The proposed device was then applied to the determination of biogenic amines in blood samples. The results obtained were in good agreement with those obtained with the GC-MS reference method.

Amplified detection of streptomycin using aptamer-conjugated palladium nanoparticles decorated on chitosan-carbon nanotube.

PubMed

Aghajari, Rozita; Azadbakht, Azadeh

2018-04-15

A streptomycin-specific aptamer was used as a receptor molecule for ultrasensitive quantitation of streptomycin. The glassy carbon (GC) electrode was modified with palladium nanoparticles decorated on chitosan-carbon nanotube (PdNPs/CNT/Chi) and aminated aptamer against streptomycin. Modification of the sensing interface was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray (EDS), wavelength-dispersive X-ray spectroscopy (WDX), cyclic voltammetry (CVs), and electrochemical impedance spectroscopy (EIS). The methodologies applied for designing the proposed biosensor are based on target-induced conformational changes of streptomycin-specific aptamer, leading to detectable signal change. Sensing experiments were performed in the streptomycin concentration range from 0.1 to 1500 nM in order to evaluate the sensor response as a function of streptomycin concentration. Based on the results, the charge transfer resistance (R ct ) values increased proportionally to enhanced streptomycin content. The limit of detection was found to be as low as 18 pM. The superior selectivity and affinity of aptamer/PdNPs/CNT/Chi modified electrode for streptomycin recognition made it favorable for versatile applications such as streptomycin analysis in real samples. Copyright © 2018 Elsevier Inc. All rights reserved.

Fuel blends: Enhanced electro-oxidation of formic acid in its blend with methanol at platinum nanoparticles modified glassy carbon electrodes

NASA Astrophysics Data System (ADS)

El-Deab, Mohamed S.; El-Nagar, Gumaa A.; Mohammad, Ahmad M.; El-Anadouli, Bahgat E.

2015-07-01

The current study addresses, for the first time, the enhanced direct electro-oxidation of formic acid (FA) at platinum-nanoparticles modified glassy carbon (nano-Pt/GC) electrode in the presence of methanol (MeOH) as a blending fuel. This enhancement is probed by: (i) the increase of the direct oxidation current of FA to CO2 (Ipd, dehydrogenation pathway), (ii) suppressing the dehydration pathway (Ipind, producing the poisoning intermediate CO) and (iii) a favorable negative shift of the onset potential of Ipd with increasing the mole fraction of MeOH in the blend. Furthermore, the charge of the direct FA oxidation in 0.3 M FA + 0.3 M MeOH blend is by 14 and 21times higher than that observed for 0.3 M FA and 0.3 M MeOH, respectively. MeOH is believed to adsorb at the Pt surface sites and thus disfavor the "non-faradaic" dissociation of FA (which produces the poisoning CO intermediate), i.e., MeOH induces a high CO tolerance of the Pt catalyst. The enhanced oxidation activity indicates that FA/MeOH blend is a promising fuel system.

Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate.

PubMed

Carino, Emily V; Newman, Daniel J; Connell, Justin G; Kim, Chaerin; Brushett, Fikile R

2017-10-31

Irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6 ) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double-layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity in organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6× increase in roughness, in good agreement with the changes in double-layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double-layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. These results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.

Impedance dispersion analysis of drug-membrane interactions

NASA Astrophysics Data System (ADS)

Tacheva, Bilyana; Paarvanova, Boyana; Ivanov, Ivan T.; Karabaliev, Miroslav

2017-11-01

Thin lipid films modified glassy carbon electrodes (GCE) were used in this work as model system for studying the interactions between two antipsychotic phenothiazine drugs, chlorpromazine and thioridazine, and the lipid fraction of the biomembranes. The lipid films on the electrode surface were obtained through the thinning of film-forming lipid solution deposited between an electrolyte phase and the working GC electrode. The effects of the drugs on the lipid film structure were investigated by electrochemical impedance spectroscopy (EIS). To characterize the electric properties of the lipid film the impedance of the working GCE is modeled with an equivalent circuit consisting of parallel capacitance Cp and resistance Rp. These capacitance and resistance are not frequency independent but could be calculated as equivalent Cp and Rp for each measured frequency of the impedance spectrum and presented as functions of the frequency f, Cp = Cp(f) and Rp= Rp(f). For the lipid films used in this work, it is demonstrated that both Cp(f) and Rp(f) are well approximated with power-law functions. This behavior implies that the impedance Z of the films could be analysed in terms of the well-known constant-phase angle element (CPE), which is often used to describe the interfacial impedance of solid working electrodes.

Synthesis of Nitrogen-Doped Graphene Quantum Dots at Low Temperature for Electrochemical Sensing Trinitrotoluene.

PubMed

Cai, Zhewei; Li, Fumin; Wu, Ping; Ji, Lijuan; Zhang, Hui; Cai, Chenxin; Gervasio, Dominic F

2015-12-01

Nitrogen-doped graphene quantum dots (N-GQDs) are synthesized at low temperature as a new catalyst allowing electrochemical detection of 2,4,6-trinitrotoluene (TNT). N-GQDs are made by an oxidative ultrasonication of graphene oxide (GO) forming nanometer-sized species, which are then chemically reduced and nitrogen doped by reacting with hydrazine. The as-synthesized N-GQDs have an average diameter of ∼2.5 nm with an N/C atomic ratio of up to ∼6.4%. To detect TNT, TNT is first accumulated on N-GQDs modified glassy carbon (N-GQDs/GC) electrode by holding the electrode at a 0 V versus Ag/AgCl for 150 s in an aqueous TNT solution. Next, the N-GQDs/GC electrode with accumulated TNT is transferred to a fresh PBS solution (0.1 M, pH 7.0, without TNT), where the TNT reduction current at -0.36 V versus Ag/AgCl in a linear scan voltammogram (LSV) shows a linear response to TNT concentration in the aqueous solution from 1 to 400 ppb, with a correlation coefficient of 0.999, a detection limit of 0.2 ppb at a signal/noise (S/N) of 3, and a detection sensitivity of 363 ± 7 mA mM(-1) cm(-2). The detection limit of 0.2 ppb of TNT for this new method is much lower than 2 ppb set by the U.S. Environmental Protection Agency for drinking water. Therefore, N-GQDs allow an electrochemical method for assaying TNT in drinking water to determine if levels of TNT are safe or not.

Removal of urea from dilute streams using RVC/nano-NiO x -modified electrode.

PubMed

Tammam, Reham H; Touny, Ahmed H; Saleh, Mahmoud M

2018-05-08

Reticulated vitreous carbon (RVC), a high surface area electrode (40 cm 2 /cm 3 ), has been modified with nickel oxide nanoparticles (nano-NiO x ) and used for electrochemical oxidation of urea from alkaline solution. For the cyclic voltammetry measurements, the used dimensions are 0.8 cm × 0.8 cm × 0.3 cm. The purpose was to offer high specific surface area using a porous open network structure to accelerate the electrochemical conversion. NiO x nanoparticles have been synthesized via an electrochemical route at some experimental conditions. The morphological, structural, and electrochemical properties of the RVC/nano-NiO x are characterized by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), cyclic voltammetry (CV), and potentiostatic measurements. The fabricated electrode, RVC/nano-NiO x , demonstrates high electrocatalytic activity towards urea oxidation in an alkaline electrolyte. The onset potential of the RVC/nano-NiO x compared to that of the planar GC/NiO x is shifted to more negative value with higher specific activity. The different loadings of the NiO x have a substantial influence on the conversion of urea which has been evaluated from concentration-time curves. The urea concentration decreases with time to a limit dependent on the loading extent. Maximum conversion is obtained at 0.86 mg of NiO x per cm 3 of the RVC matrix.

2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction.

PubMed

Rowley-Neale, Samuel J; Fearn, Jamie M; Brownson, Dale A C; Smith, Graham C; Ji, Xiaobo; Banks, Craig E

2016-08-21

Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm(-2) modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.

Electroreduction of Er 3+ in nonaqueous solvents

DOE PAGES

Small, Leo J.; Sears, Jeremiah M.; Lambert, Timothy N.; ...

2016-09-15

Here, the electroreduction of Er 3+ in propylene carbonate, N,N-dimethylformamide, or a variety of quaternary ammonium ionic liquids (ILs) was investigated using [Er(OTf) 3] and [Er(NTf 2) 3]. Systematic variation of the ILs' cation and anion, Er 3+ salt, and electrode material revealed a disparity in electrochemical interactions not previously seen. For most ILs at a platinum electrode, cyclic voltammetry exhibits irreversible interactions between Er 3+ salts and the electrode at potentials significantly less than the theoretical reduction potential for Er 3+. Throughout all solvent–salt systems tested, a deposit could be formed on the electrode, though obtaining a high purity,more » crystalline Er 0 deposit is challenging due to the extreme reactivity of the deposit and resulting chemical interactions, often resulting in the formation of a complex, amorphous solid–electrolyte interface that slowed deposition rates. Comparison of platinum, gold, nickel, and glassy carbon (GC) working electrodes revealed oxidation processes unique to the platinum surface. While no appreciable reduction current was observed on GC at the potentials investigated, deposits were seen on platinum, gold, and nickel electrodes.« less

Schiff Base modified on CPE electrode and PCB gold electrode for selective determination of silver ion

NASA Astrophysics Data System (ADS)

Leepheng, Piyawan; Suramitr, Songwut; Phromyothin, Darinee

2017-09-01

The schiff base was synthesized by 2,5-thiophenedicarboxaldehyde and 1,2,4-thiadiazole-3,5-diamine with condensation method. There was modified on carbon paste electrode (CPE) and Printed circuit board (PCB) gold electrode for determination silver ion. The schiff base modified electrodes was characterized by atomic force microscopy (AFM) and scanning electron microscopy (SEM), respectively. The electrochemical study was reported by cyclic voltammetry method and impedance spectroscopy using modified electrode as working electrode, platinum wire and Ag/AgCl as counter electrode and reference electrode, respectively. The modified electrodes have suitable detection for Ag+. The determination of silver ions using the modified electrodes depended linearly on Ag+ concentration in the range 1×10-10 M to 1×10-7 M, with cyclic voltammetry sensitivity were 2.51×108 μAM-1 and 1.88×108 μAM-1 for PCB gold electrode and CPE electrode, respectively, limits of detection were 5.33×10-9 M and 1.99×10-8 M for PCB gold electrode and CPE electrode, respectively. The modified electrodes have high accuracy, inexpensive and can applied to detection Ag+ in real samples.

Anti-tumor response with immunologically modified carbon nanotubes and phototherapy

NASA Astrophysics Data System (ADS)

Acquaviva, Joseph T.; Zhou, Feifan; Boarman, Ellen; Chen, Wei R.

2013-02-01

While successes of different cancer therapies have been achieved in various degrees a systemic immune response is needed to effectively treat late-stage, metastatic cancers, and to establish long-term tumor resistance in the patients. A novel method for combating metastatic cancers has been developed using immunologically modified carbon nanotubes in conjunction with phototherapy. Glycated chitosan (GC) is a potent immunological adjuvant capable of increasing host immune responses, including antigen presentation by activation of dendritic cells (DCs) and causing T cell proliferation. GC is also an effective surfactant for nanomaterials. By combining single-walled carbon nanotubes (SWNTs) and GC, immunologically modified carbon nanotubes (SWNT-GC) were constructed. The SWNT-GC suspension retains the enhanced light absorption properties in the near infrared (NIR) region and the ability to enter cells, which are characteristic of SWNTs. The SWNT-GC also retains the immunological properties of GC. Cellular SWNT-GC treatments increased macrophage activity, DC activation and T cell proliferation. When cellular SWNT-GC was irradiated with a laser of an appropriate wavelength, these immune activities could be enhanced. The combination of laser irradiation and SWNT-GC induced cellular toxicity in targeted tumor cells, leading to a systemic antitumor response. Immunologically modified carbon nanotubes in conjunction with phototherapy is a novel and promising method to produce a systemic immune response for the treatment of metastatic cancers.

Platinum nanoparticles decorated dendrite-like gold nanostructure on glassy carbon electrodes for enhancing electrocatalysis performance to glucose oxidation

NASA Astrophysics Data System (ADS)

Jia, Hongmei; Chang, Gang; Lei, Ming; He, Hanping; Liu, Xiong; Shu, Honghui; Xia, Tiantian; Su, Jie; He, Yunbin

2016-10-01

Platinum nanoparticles decorated dendrite-like gold nanostructure, bimetal composite materials on glassy carbon electrode (Pt/DGNs/GC) for enhancing electrocatalysis to glucose oxidation was designed and successfully fabricated by a facile two-step deposition method without any templates, surfactants, or stabilizers. Dendrite-like gold nanostructure was firstly deposited on the GC electrode via the potentiostatic method, and then platinum nanoparticles were decorated on the surface of gold substrate through chemical reduction deposition. X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDS) were applied to characterize the evolution of morphology and structure of the as-prepared Pt/DGNs/GC. Based on electrochemical measurements such as cyclic voltammetry, linear voltammetry and chronoamperometry, Pt/DGNs/GC exhibited significantly enhanced electrocatalytic performance to glucose oxidation compared those of pure dendrite-like Au nanoparticles in our previous report. Controlling chemical reduction deposition time, the amount of platinum nanoparticles on Au surface could be regulated, which further tuned electrocatalytic properties toward glucose oxidation. The dendrite-like gold surface partially covered by platinum nanoparticles dramatically enhanced the electrocatalytic performance for the oxidation of glucose because of excellent synergetic effects between gold and platinum species and the increased electrochemical active area from Pt nanoparticles loading. The non-enzymatic glucose biosensor based on Pt/DGNs/GC showed a rapid respond time (within 2 s), wide linear range (from 0.1 mM to 14 mM), low detection limit (0.01 mM), supernal sensitivity (275.44 μA cm-2 mM-1, R = 0.993), satisfactory reproducibility and good stability for glucose sensing. It was demonstrated that Pt/DGNs/GC could work as promising candidate for factual non-enzymatic glucose detection.

A Comparative evaluation of Graphene oxide based materials for Electrochemical non-enzymatic sensing of Curcumin

NASA Astrophysics Data System (ADS)

Dey, Nibedita; Devasena, T.; Sivalingam, Tamilarasu

2018-02-01

This work reports a comparative study on the development of a sensitive voltammetric method for the assay of diferuloylmethane which is fabricated using cost-effective sensing material graphene oxide (GO modified electrode) and reduced graphene oxide (rGO modified electrode) modified on glassy carbon electrode respectively. The prepared materials were characterized using SEM, XRD, FTIR, and Raman techniques to understand the formation. Between the both modified electrodes, rGO modified electrode demonstrated a lower limit detection of 0.9 pM and good signal quality. But, the better linear dynamic range for detection was found to be 1 nm to 100 nM for GO and 0.1 nM to 10 nM for rGO modified electrodes respectively. The repeatability is checked for seven cycles and interference studies were also performed for checking the sensors’ selectivity to curcumin. rGO modified electrode and GO modified electrode both shows specific signals for Diferuloylmethane under conditions similar to physiology. But, with better properties over GO modified electrode, rGO modified electrode is suggested a better candidate for real-time usability in sensing. The detection limit reported is the lowest till date for the given plant drug using any sensing assay.

Non-platinum metal-organic framework based electro-catalyst for promoting oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Das, Dipanwita; Raut, Vrushali; Kireeti, Kota V. M. K.; Jha, Neetu

2018-04-01

We developed two non-precious Metal Organic Framework (MOF) based electrocatalysts, MOF-5 and MOF-i using solvothermal and refluxing methods. The MOFs prepared has been characterized by powder X-ray diffractometer (XRD), Fourier Transform Infra-Red Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) for structural and morphological insights. SEM images reveal cubic shape for solvothermally synthesized MOF-5, whereas refluxing method leads to platelet morphology of MOF-i. The synthesized MOFs has been investigated for Oxygen Reduction Reaction (ORR) studies using Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV), with MOF modified Glassy Carbon (GC) as working electrode. The electrochemical data suggests higher activity of MOF-5 towards ORR compared to MOF-i.

Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate

DOE PAGES

Carino, Emily V.; Newman, Daniel J.; Connell, Justin G.; ...

2017-09-19

In this paper, irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double -layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity inmore » organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6X increase in roughness, in good agreement with the changes in double -layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double -layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. Lastly, these results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.« less

Charge transport and ac response under light illumination in gate-modulated DNA molecular junctions.

PubMed

Zhang, Yan; Zhu, Wen-Huan; Ding, Guo-Hui; Dong, Bing; Wang, Xue-Feng

2015-05-22

Using a two-strand tight-binding model and within nonequilibrium Green's function approach, we study charge transport through DNA sequences (GC)NGC and (GC)1(TA)NTA (GC)3 sandwiched between two Pt electrodes. We show that at low temperature DNA sequence (GC)NGC exhibits coherent charge carrier transport at very small bias, since the highest occupied molecular orbital in the GC base pair can be aligned with the Fermi energy of the metallic electrodes by a gate voltage. A weak distance dependent conductance is found in DNA sequence (GC)1(TA)NTA (GC)3 with large NTA. Different from the mechanism of thermally induced hopping of charges proposed by the previous experiments, we find that this phenomenon is dominated by quantum tunnelling through discrete quantum well states in the TA base pairs. In addition, ac response of this DNA junction under light illumination is also investigated. The suppression of ac conductances of the left and right lead of DNA sequences at some particular frequencies is attributed to the excitation of electrons in the DNA to the lead Fermi surface by ac potential, or the excitation of electrons in deep DNA energy levels to partially occupied energy levels in the transport window. Therefore, measuring ac response of DNA junctions can reveal a wealth of information about the intrinsic dynamics of DNA molecules.

Carbon/CuO nanosphere-anchored g-C3N4 nanosheets as ternary electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Vattikuti, S. V. Prabhakar; Reddy, B. Purusottam; Byon, Chan; Shim, Jaesool

2018-06-01

Novel electrode materials for supercapacitors comprised of carbon and copper oxide (CuO) nanospheres on graphitic carbon nitride (g-C3N4) nanosheets, denoted as C/CuO@g-C3N4 are self-assembled via a one-step co-pyrolysis decomposition method. The pure g-C3N4 and C/CuO@g-C3N4 were confirmed by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), thermal gravimetric and differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption studies and Fourier-transform infrared spectroscopy (FTIR). The specific capacitance was 247.2 F g-1 in 0.5 M NaOH at a current density of 1 A g-1, and more than 92.1% of the capacitance was retained after 6000 cycles. The property enhancement was ascribed to the synergistic effects of the three components in the composite. These results suggest that C/CuO@g-C3N4 possessed an excellent cyclic stability with respect to their capacity performance as electrode materials.

Imidazole modified g-C3N4 photocatalyst: Structural characterization and versatile energy applications

NASA Astrophysics Data System (ADS)

Zhang, Lu; Liu, Qianqian; Chai, Yuanyuan; Ren, Jia; Dai, Wei-Lin

2018-02-01

Novel imidazole modified g-C3N4 were firstly synthesized via a facile one-pot thermo-induced co-condensation method. Characterization results showed that imidazole modification can improve the visible light harvesting, interfacial charge transfer and separation of g-C3N4, without destroying its pristine framework structure. The as-obtained imidazole modified g-C3N4 showed remarkably enhanced and rather stable photocatalytic performance in H2 evolution, photo-degradation of water contaminants and selective photo-oxidation of benzyl alcohol, demonstrating its all-round applications as a versatile photocatalyst. The weight ratio between imidazole and urea was well tuned and the optimal photocatalytic activity was obtained, which shows CNU-I50 sample (50 mg imidazole in 15 g urea) possesses the highest hydrogen evolution rate of 2150 μmol g-1 h-1, superior to most of the previous reported g-C3N4 materials. These results suggest that those imidazole modified g-C3N4 materials are potential photocatalyst when applied to solar energy conversion, water purification and selective photosynthesis reactions.

Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harnisch, Jennifer Anne

2001-01-01

The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performancemore » both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol (BHT) SAMs. BHT chemisorbs to the gold surface in a previously unprecedented planar fashion. Carbon and gold substrates can be chemically altered by several methodologies resulting in new surface properties. The development of modification protocols and their application in the analytical arena is considered herein.« less

Probing Electrode Heterogeneity Using Fourier-Transformed Alternating Current Voltammetry: Application to a Dual-Electrode Configuration.

PubMed

Tan, Sze-Yin; Unwin, Patrick R; Macpherson, Julie V; Zhang, Jie; Bond, Alan M

2017-03-07

Quantitative studies of electron transfer processes at electrode/electrolyte interfaces, originally developed for homogeneous liquid mercury or metallic electrodes, are difficult to adapt to the spatially heterogeneous nanostructured electrode materials that are now commonly used in modern electrochemistry. In this study, the impact of surface heterogeneity on Fourier-transformed alternating current voltammetry (FTACV) has been investigated theoretically under the simplest possible conditions where no overlap of diffusion layers occurs and where numerical simulations based on a 1D diffusion model are sufficient to describe the mass transport problem. Experimental data that meet these requirements can be obtained with the aqueous [Ru(NH 3 ) 6 ] 3+/2+ redox process at a dual-electrode system comprised of electrically coupled but well-separated glassy carbon (GC) and boron-doped diamond (BDD) electrodes. Simulated and experimental FTACV data obtained with this electrode configuration, and where distinctly different heterogeneous charge transfer rate constants (k 0 values) apply at the individual GC and BDD electrode surfaces, are in excellent agreement. Principally, because of the far greater dependence of the AC current magnitude on k 0 , it is straightforward with the FTACV method to resolve electrochemical heterogeneities that are ∼1-2 orders of magnitude apart, as applies in the [Ru(NH 3 ) 6 ] 3+/2+ dual-electrode configuration experiments, without prior knowledge of the individual kinetic parameters (k 0 1 and k 0 2 ) or the electrode size ratio (θ 1 :θ 2 ). In direct current voltammetry, a difference in k 0 of >3 orders of magnitude is required to make this distinction.

Surface modification of amine-functionalised graphite for preparation of cobalt hexacyanoferrate (CoHCF)-modified electrode: an amperometric sensor for determination of butylated hydroxyanisole (BHA).

PubMed

Prabakar, S J Richard; Narayanan, S Sriman

2006-12-01

A cobalt hexacyanoferrate (CoHCF)-modified graphite paraffin wax composite electrode was prepared by a new approach. An amine-functionalised graphite powder was used for the fabrication of the electrode. A functionalised graphite paraffin wax composite electrode was prepared and the surface of the electrode was modified with a thin film of CoHCF. Various parameters that influence the electrochemical behaviour of the modified electrode were studied by varying the background electrolytes, scan rates and pH. The modified electrode showed good electrocatalytic activity towards the oxidation of butylated hydroxyanisole (BHA) under optimal conditions and showed a linear response over the range from 7.9 x 10(-7) to 1.9 x 10(-4) M of BHA with a correlation coefficient of 0.9988. The limit of detection was 1.9 x 10(-7) M. Electrocatalytic oxidation of BHA was effective at the modified electrode at a significantly reduced potential and at a broader pH range. The utility of the modified electrode as an amperometric sensor for the determination of BHA in flow systems was evaluated by carrying out hydrodynamic and chronoamperometric experiments. The modified electrode showed very good stability and a longer shelf life. The modified electrode was applied for the determination of BHA in spiked samples of chewing gum and edible sunflower oil. The advantage of this method is the ease of electrode fabrication, good stability, longer shelf life, low cost and its diverse application for BHA determination.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carino, Emily V.; Newman, Daniel J.; Connell, Justin G.

In this paper, irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double -layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity inmore » organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6X increase in roughness, in good agreement with the changes in double -layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double -layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. Lastly, these results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.« less

Fabrication of an electrochemical platform based on the self-assembly of graphene oxide-multiwall carbon nanotube nanocomposite and horseradish peroxidase: direct electrochemistry and electrocatalysis

NASA Astrophysics Data System (ADS)

Zhang, Qian; Yang, Shaojun; Zhang, Jing; Zhang, Ling; Kang, Pingli; Li, Jinghong; Xu, Jingwei; Zhou, Hua; Song, Xi-Ming

2011-12-01

A novel hybrid nanomaterial (GO-MWNTs) was explored based on the self-assembly of multiwall carbon nanotubes (MWNTs) and graphene oxide (GO). Compared with pristine MWNTs, such a nanocomposite could be well dispersed in aqueous solution and exhibit a negative charge. Driven by the electrostatic interaction, positively charged horseradish peroxidase (HRP) could then be immobilized onto GO-MWNTs at the surface of a glassy carbon (GC) electrode to form a HRP/GO-MWNT/GC electrode under mild conditions. TEM was used to characterize the morphology of the GO-MWNT nanocomposite. UV-vis and FTIR spectra suggested that HRP was immobilized onto the hybrid matrix without denaturation. Furthermore, the immobilized HRP showed enhanced direct electron transfer for the HRP-Fe(III)/Fe(II) redox center. Based on the direct electron transfer of the immobilized HRP, the HRP/GO-MWNT/GC electrode exhibited excellent electrocatalytic behavior to the reduction of H2O2 and NaNO2, respectively. Therefore, GO-MWNTs could provide a novel and efficient platform for the immobilization and biosensing of redox enzymes, and thus may find wide potential applications in the fabrication of biosensors, biomedical devices, and bioelectronics.

g-C3N4 modified TiO2 nanosheets with enhanced photoelectric conversion efficiency in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Xu, Jian; Wang, Guanxi; Fan, Jiajie; Liu, Baoshun; Cao, Shaowen; Yu, Jiaguo

2015-01-01

Dye-sensitized solar cells (DSSCs) were fabricated by using g-C3N4 modified TiO2 nanosheets (CTS) as photoanode materials in this research. A thin layer of g-C3N4 was coated on the surface of TiO2 nanosheets by simply heating the mixture of TiO2 nanosheets and urea, which led to the formation of TiO2@g-C3N4 nanosheet heterostructure. The experimental results showed that the photoelectric conversion efficiency of DSSCs was obviously improved after modified by g-C3N4. The measurements of I-V characteristic indicated that the introduction of g-C3N4 could increase both the open circuit voltage and short-circuit photocurrent density. Along with the analysis of electrochemical impedance spectroscopy, it is considered that the thin layer of g-C3N4 can act as the blocking layer for electron backward recombination with electrolyte, which can be used as the functional material to increase the DSSC performance.

Application of high-frequency Granger causality to analysis of epileptic seizures and surgical decision making.

PubMed

Epstein, Charles M; Adhikari, Bhim M; Gross, Robert; Willie, Jon; Dhamala, Mukesh

2014-12-01

In recent decades intracranial EEG (iEEG) recordings using increasing numbers of electrodes, higher sampling rates, and a variety of visual and quantitative analyses have indicated the presence of widespread, high frequency ictal and preictal oscillations (HFOs) associated with regions of seizure onset. Seizure freedom has been correlated with removal of brain regions generating pathologic HFOs. However, quantitative analysis of preictal HFOs has seldom been applied to the clinical problem of planning the surgical resection. We performed Granger causality (GC) analysis of iEEG recordings to analyze features of preictal seizure networks and to aid in surgical decision making. Ten retrospective and two prospective patients were chosen on the basis of individually stereotyped seizure patterns by visual criteria. Prospective patients were selected, additionally, for failure of those criteria to resolve apparent multilobar ictal onsets. iEEG was recorded at 500 or 1,000 Hz, using up to 128 surface and depth electrodes. Preictal and early ictal GC from individual electrodes was characterized by the strength of causal outflow, spatial distribution, and hierarchical causal relationships. In all patients we found significant, widespread preictal GC network activity at peak frequencies from 80 to 250 Hz, beginning 2-42 s before visible electrographic onset. In the two prospective patients, GC source/sink comparisons supported the exclusion of early ictal regions that were not the dominant causal sources, and contributed to planning of more limited surgical resections. Both patients have a class 1 outcome at 1 year. GC analysis of iEEG has the potential to increase understanding of preictal network activity, and to help improve surgical outcomes in cases of otherwise ambiguous iEEG onset. Wiley Periodicals, Inc. © 2014 International League Against Epilepsy.

Photocatalytic, antimicrobial activities of biogenic silver nanoparticles and electrochemical degradation of water soluble dyes at glassy carbon/silver modified past electrode using buffer solution.

PubMed

Khan, Zia Ul Haq; Khan, Amjad; Shah, Afzal; Chen, Yongmei; Wan, Pingyu; Khan, Arif Ullah; Tahir, Kamran; Muhamma, Nawshad; Khan, Faheem Ullah; Shah, Hidayat Ullah

2016-03-01

In the present research work a novel, nontoxic and ecofriendly procedure was developed for the green synthesis of silver nano particle (AgNPs) using Caruluma edulis (C. edulis) extract act as reductant as well as stabilizer agents. The formation of AgNPs was confirmed by UV/Vis spectroscopy. The small and spherical sizes of AgNPs were conformed from high resolution transmission electron microscopy (HRTEM) analysis and were found in the range of 2-10nm, which were highly dispersion without any aggregation. The crystalline structure of AgNPs was conformed from X-ray diffraction (XRD) analysis. For the elemental composition EDX was used and FTIR helped to determine the type of organic compounds in the extract. The potential electrochemical property of modified silver electrode was also studied. The AgNPs showed prominent antibacterial motion with MIC values of 125 μg/mL against Bacillus subtilis and Staphylococcus aureus while 250 μg/mL against Escherichia coli. High cell constituents' release was exhibited by B. subtilis with 2 × MIC value of silver nanoparticles. Silver nanoparticles also showed significant DPPH free radical scavenging activity. This research would have an important implication for the synthesis of more efficient antimicrobial and antioxidant agent. The AgNP modified electrode (GC/AgNPs) exhibited an excellent electro-catalytic activity toward the redox reaction of phenolic compounds. The AgNPs were evaluated for electrochemical degradation of bromothymol blue (BTB) dyes which showed a significant activity. From the strong reductive properties it is obvious that AgNPs can be used in water sanitization and converting some organic perilous in to non-hazardous materials. The AgNPs showed potential applications in the field of electro chemistry, sensor, catalyst, nano-devices and medical. Copyright © 2016 Elsevier B.V. All rights reserved.

Cobalt Phthalocyanine Modified Electrodes Utilised in Electroanalysis: Nano-Structured Modified Electrodes vs. Bulk Modified Screen-Printed Electrodes

PubMed Central

Foster, Christopher W.; Pillay, Jeseelan; Metters, Jonathan P.; Banks, Craig E.

2014-01-01

Cobalt phthalocyanine (CoPC) compounds have been reported to provide electrocatalytic performances towards a substantial number of analytes. In these configurations, electrodes are typically constructed via drop casting the CoPC onto a supporting electrode substrate, while in other cases the CoPC complex is incorporated within the ink of a screen-printed sensor, providing a one-shot economical and disposable electrode configuration. In this paper we critically compare CoPC modified electrodes prepared by drop casting CoPC nanoparticles (nano-CoPC) onto a range of carbon based electrode substrates with that of CoPC bulk modified screen-printed electrodes in the sensing of the model analytes l-ascorbic acid, oxygen and hydrazine. It is found that no “electrocatalysis” is observed towards l-ascorbic acid using either of these CoPC modified electrode configurations and that the bare underlying carbon electrode is the origin of the obtained voltammetric signal, which gives rise to useful electroanalytical signatures, providing new insights into literature reports where “electrocatalysis” has been reported with no clear control experiments undertaken. On the other hand true electrocatalysis is observed towards hydrazine, where no such voltammetric features are witnessed on the bare underlying electrode substrate. PMID:25414969

Modified g-C3N4/TiO2 nanosheets/ZnO ternary facet coupled heterojunction for photocatalytic degradation of p-toluenesulfonic acid (p-TSA) under visible light

NASA Astrophysics Data System (ADS)

Jiang, Dong; Yu, Han; Yu, Hongbing

2017-01-01

Novel ternary nanocomposites with facet coupled structure were synthesized by using modified g-C3N4, TiO2 nanosheets and nano-ZnO. Nanosheet/nanosheet heterojunction structure was investigated by TEM, XPS and XRD. FT-IR and Nitrogen adsorption were illustrated for chemical/physical structure analyses. Solution of p-Toluenesulfonic acid (p-TSA) was chosen as target pollutant for visible light photodegradation and the excellent removal efficiency was achieved by this structurally modified g-C3N4/TiO2/ZnO hybrid. The visible light absorption improvement and quantum efficiency enhancement, which were testified by UV-vis DRS, PL and p-TSA photodegradation measurements, due to the facet coupled structure and appropriate quantity of modified g-C3N4 in the nanocomposites.

Improvement of the electrochromic response of a low-temperature sintered dye-modified porous electrode using low-resistivity indium tin oxide nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watanabe, Yuichi, E-mail: yuichi.watanabe@aist.go.jp; Suemori, Kouji; Hoshino, Satoshi

2016-06-15

An indium tin oxide (ITO) nanoparticle-based porous electrode sintered at low temperatures was investigated as a transparent electrode for electrochromic displays (ECDs). The electrochromic (EC) response of the dye-modified ITO porous electrode sintered at 150 °C, which exhibited a generally low resistivity, was markedly superior to that of a conventional dye-modified TiO{sub 2} porous electrode sintered at the same temperature. Moreover, the EC characteristics of the dye-modified ITO porous electrode sintered at 150 °C were better than those of the high-temperature (450 °C) sintered conventional dye-modified TiO{sub 2} porous electrode. These improvements in the EC characteristics of the dye-modified ITO porous electrode aremore » attributed to its lower resistivity than that of the TiO{sub 2} porous electrodes. In addition to its sufficiently low resistivity attained under the sintering conditions required for flexible ECD applications, the ITO porous film had superior visible-light transparency and dye adsorption capabilities. We conclude that the process temperature, resistivity, optical transmittance, and dye adsorption capability of the ITO porous electrode make it a promising transparent porous electrode for flexible ECD applications.« less

Preparation of Fe2O3-Clorprenaline/Tetraphenylborate Nanospheres and Their Application as Ion Selective Electrode for Determination of Clorprenaline in Pork

NASA Astrophysics Data System (ADS)

Shao, Xintian; Zhang, Jing; Li, Donghui; Yue, Jingli; Chen, Zhenhua

2016-04-01

A novel modified ion selective electrode based on Fe2O3-clorprenaline/tetraphenylborate nanospheres (Fe2O3-CLPT NSs) as electroactive materials for the determination of clorprenaline hydrochloride (CLP) is described. The α-Fe2O3 nanoparticles (NPs) were prepared by hydrothermal synthesis, then self-assembled on CLP/tetraphenylborate (TPB) to form Fe2O3-CLPT NSs, which were used as a potentiometric electrode for analyte determination innovatively. The Fe2O3-CLPT NSs modified electrode exhibited a wider concentration range from 1.0 × 10-7 to 1.0 × 10-1 mol/L and a lower detection limit of 3.7 × 10-8 mol/L compared with unmodified electrodes. The selectivity of the modified electrode was evaluated by fixed interference method. The good performance of the modified electrode such as wide pH range (2.4-6.7), fast response time (15 s), and adequate lifetime (14 weeks) indicate the utility of the modified electrode for evaluation of CLP content in various real samples. Finally, the modified electrode was successfully employed to detect CLP in pork samples with satisfactory results. These results demonstrated the Fe2O3-CLPT NSs modified electrode to be a functional and convenient method to the field of potentiometry determination of CLP in real samples.

Assembly of a Cost-Effective Anode Using Palladium Nanoparticles for Alkaline Fuel Cell Applications

ERIC Educational Resources Information Center

Feliciano-Ramos, Ileana; Casan~as-Montes, Barbara; García-Maldonado, María M.; Menendez, Christian L.; Mayol, Ana R.; Díaz-Vazquez, Liz M.; Cabrera, Carlos R.

2015-01-01

Nanotechnology allows the synthesis of nanoscale catalysts, which offer an efficient alternative for fuel cell applications. In this laboratory experiment, the student selects a cost-effective anode for fuel cells by comparing three different working electrodes. These are commercially available palladium (Pd) and glassy carbon (GC) electrodes, and…

Understanding interaction of curcumin and metal ions on electrode surfaces using EDXRF

NASA Astrophysics Data System (ADS)

Joseph, Daisy; Kumar, K. Krishna; Narayanan, S. Sriman

2018-04-01

A chemically modified electrode was developed for determination of metal ions (Cd, Pb, Zn, Co, Hg). The modifier used for the study was Curcumin. Curcumin acts as a complexing agent at the surface of the electrode for preconcentration of metal ions from electrolyte to electrode surface and stripped back to electrolyte during analysis. EDXRF was used to analyze these electrodes and it was concluded that the PCR modified electrode favored effective chelation for lead and mercury.

Fabrication of modified g-C3N4 nanorod/Ag3PO4 nanocomposites for solar-driven photocatalytic oxygen evolution from water splitting

NASA Astrophysics Data System (ADS)

Tian, Lin; Xian, Xiaozhai; Cui, Xingkai; Tang, Hua; Yang, Xiaofei

2018-02-01

Semiconductor-based photocatalysis has been considered as one of the most effective techniques to achieve the conversion of clean and sustainable sunlight to solar fuel, in which the construction of novel solar-driven photocatalytic systems is the key point. Here, we report initially the synthesis of modified graphitic carbon nitride (g-C3N4) nanorods via the calcination of intermediates obtained from the co-polymerization of precursors, and the in-situ hybridization of Ag3PO4 with as-prepared modified g-C3N4 to produce g-C3N4 nanorod/Ag3PO4 composite materials. The diameter of modified rod-like g-C3N4 materials is determined to be around 1 μm. Subsequently the morphological features, crystal and chemical structures of the assembled g-C3N4 nanorod/Ag3PO4 composites were systematically investigated by SEM, XRD, XPS, UV-vis diffuse reflectance spectra (DRS). Furthermore, the use of as-prepared composite materials as the catalyst for photocatalytic oxygen evolution from water splitting was studied. The oxygen-generating results showed that the composite photocatalyst modified with 600 mg rod-like g-C3N4 demonstrates 2.5 times higher efficiency than that of bulk Ag3PO4. The mechanism behind the enhancement in the oxygen-evolving activity is proposed on the basis of in-situ electron spin resonance (ESR) measurement as well as theoretical analysis. The study provides new insights into the design and development of new photocatalytic composite materials for energy and environmental applications.

Applications of Graphene-Modified Electrodes in Microbial Fuel Cells

PubMed Central

Yu, Fei; Wang, Chengxian; Ma, Jie

2016-01-01

Graphene-modified materials have captured increasing attention for energy applications due to their superior physical and chemical properties, which can significantly enhance the electricity generation performance of microbial fuel cells (MFC). In this review, several typical synthesis methods of graphene-modified electrodes, such as graphite oxide reduction methods, self-assembly methods, and chemical vapor deposition, are summarized. According to the different functions of the graphene-modified materials in the MFC anode and cathode chambers, a series of design concepts for MFC electrodes are assembled, e.g., enhancing the biocompatibility and improving the extracellular electron transfer efficiency for anode electrodes and increasing the active sites and strengthening the reduction pathway for cathode electrodes. In spite of the challenges of MFC electrodes, graphene-modified electrodes are promising for MFC development to address the reduction in efficiency brought about by organic waste by converting it into electrical energy. PMID:28773929

2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Rowley-Neale, Samuel J.; Fearn, Jamie M.; Brownson, Dale A. C.; Smith, Graham C.; Ji, Xiaobo; Banks, Craig E.

2016-08-01

Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr04073j

Graphitized Carbon: A Promising Stable Cathode Catalyst Support Material for Long Term PEMFC Applications.

PubMed

Mohanta, Paritosh Kumar; Regnet, Fabian; Jörissen, Ludwig

2018-05-28

Stability of cathode catalyst support material is one of the big challenges of polymer electrolyte membrane fuel cells (PEMFC) for long term applications. Traditional carbon black (CB) supports are not stable enough to prevent oxidation to CO₂ under fuel cell operating conditions. The feasibility of a graphitized carbon (GC) as a cathode catalyst support for low temperature PEMFC is investigated herein. GC and CB supported Pt electrocatalysts were prepared via an already developed polyol process. The physical characterization of the prepared catalysts was performed using transmission electron microscope (TEM), X-ray Powder Diffraction (XRD) and inductively coupled plasma optical emission spectrometry (ICP-OES) analysis, and their electrochemical characterizations were conducted via cyclic voltammetry(CV), rotating disk electrode (RDE) and potential cycling, and eventually, the catalysts were processed using membrane electrode assemblies (MEA) for single cell performance tests. Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SEM) have been used as MEA diagonostic tools. GC showed superior stability over CB in acid electrolyte under potential conditions. Single cell MEA performance of the GC-supported catalyst is comparable with the CB-supported catalyst. A correlation of MEA performance of the supported catalysts of different Brunauer⁻Emmett⁻Teller (BET) surface areas with the ionomer content was also established. GC was identified as a promising candidate for catalyst support in terms of both of the stability and the performance of fuel cell.

High activity of g-C3N4/multiwall carbon nanotube in catalytic ozonation promotes electro-peroxone process.

PubMed

Guo, Zhuang; Cao, Hongbin; Wang, Yuxian; Xie, Yongbing; Xiao, Jiadong; Yang, Jin; Zhang, Yi

2018-06-01

Three kinds of graphitic carbon nitride materials (bulk, porous and nanosheet g-C 3 N 4 ) were composited with a multiwall carbon nanotube (MWCNT) by a hydrothermal method, and the obtained b-C 3 N 4 /CNT, p-C 3 N 4 /CNT and n-C 3 N 4 /CNT materials were used in the electrodes for electro-peroxone process. It was found that the n-C 3 N 4 /CNT composite exhibited the highest efficiency in oxalate degradation, though it performed the worst in the oxygen-reduction reaction for H 2 O 2 production. The n-C 3 N 4 /CNT composite exhibited higher activity than CNT and other composites in catalytic ozonation experiments, due to the higher pyrrolic-N content modified on the CNT surface and higher surface area. It also has higher electron transfer ability, which benefited to the electro-reduction of both O 2 and O 3 . The result confirmed that catalytic ozonation process was an important means to enhance the degradation efficiency in the electro-peroxone process, besides peroxone process and O 3 -electrolysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Simultaneous determination of hydroxylamine and phenol using a nanostructure-based electrochemical sensor.

PubMed

Moghaddam, Hadi Mahmoudi; Beitollahi, Hadi; Tajik, Somayeh; Malakootian, Mohammad; Maleh, Hassan Karimi

2014-11-01

The electrochemical oxidation of hydroxylamine on the surface of a carbon paste electrode modified with carbon nanotubes and 2,7-bis(ferrocenyl ethyl)fluoren-9-one is studied. The electrochemical response characteristics of the modified electrode toward hydroxylamine and phenol were investigated. The results showed an efficient catalytic activity of the electrode for the electro-oxidation of hydroxylamine, which leads to lowering its overpotential. The modified electrode exhibits an efficient electron-mediating behavior together with well-separated oxidation peaks for hydroxylamine and phenol. Also, the modified electrode was used for determination of hydroxylamine and phenol in some real samples.

Chemically modified graphite for electrochemical cells

DOEpatents

Greinke, R.A.; Lewis, I.C.

1998-05-26

This invention relates to chemically modified graphite particles: (a) that are useful in alkali metal-containing electrode of a electrochemical cell comprising: (1) the electrode, (2) a non-aqueous electrolytic solution comprising an organic aprotic solvent which solvent tends to decompose when the electrochemical cell is in use, and an electrically conductive salt of an alkali metal, and (3) a counter electrode; and (b) that are chemically modified with fluorine, chlorine, iodine or phosphorus to reduce such decomposition. This invention also relates to electrodes comprising such chemically modified graphite and a binder and to electrochemical cells containing such electrodes. 3 figs.

Improvement on the Repair Effect of Electrochemical Chloride Extraction Using a Modified Electrode Configuration

PubMed Central

Feng, Wei; Xu, Jinxia; Jiang, Linhua; Song, Yingbin; Cao, Yalong; Tan, Qiping

2018-01-01

To improve the repair effect of electrochemical chloride extraction, a modified electrode configuration is applied in this investigation. In this configuration, two auxiliary electrodes placed in the anodic and cathodic electrolytes were used as the anode and cathode, respectively. Besides this, the steel in the mortar was grounded to protect it from corrosion. By a comparative experiment, the potential evolution, various ions concentrations (Cl−, OH−, Na+, and K+) in different mortar depths, the corrosion potential, and the current density of the steel were measured. The results indicate that compared to electrochemical chloride extraction with the traditional electrode configuration, this electrochemical chloride extraction method with a modified electrode configuration has a similar chloride removal ratio. Besides this, potential of steel is just about 800 mV for a saturated calomel electrode (SCE) during the treatment, which did not reach the hydrogen evolution potential. The phenomenon of the accumulation of OH−, Na+, and K+ did not occur when the modified electrode configuration is applied. Additionally, higher corrosion potentials and lower corrosion current rates were measured after performing electrochemical chloride extraction with the modified electrode configuration. Additionally, it is a short period of time for the steel to go from activation to passivation. On this basis, the modified electrode configuration may overcome the drawbacks of electrochemical chloride extraction. PMID:29389855

Fabrication, characterisation and voltammetric studies of gold amalgam nanoparticle modified electrodes.

PubMed

Welch, Christine M; Nekrassova, Olga; Dai, Xuan; Hyde, Michael E; Compton, Richard G

2004-09-20

The tabrication, characterisation, and electroanalytical application of gold and gold amalgam nanoparticles on glassy carbon electrodes is examined. Once the deposition parameters for gold nanoparticle electrodes were optimised, the analytical utility of the electrodes was examined in CrIII electroanalysis. It was found that gold nanoparticle modified (Au-NM) electrodes possess higher sensitivity than gold macroelectrodes. In addition, gold amalgam nanoparticle modified (AuHg-NM) electrodes were fabricated and characterised. The response of those electrodes was recorded in the presence of important environmental analytes (heavy metal cations). It was found AuHg-NM electrodes demonstrate a unique voltammetric behaviour and can be applied for electroanalysis when enhanced sensitivity is crucial.

CHROMIUM ELECTROANALYSIS AT SCREEN PRINTED ELECTRODE MODIFIED BY THIN FILMS OF NICKEL

EPA Science Inventory

A rapid and potentially cost-effective electrochemical method is reported for analysis of chromium (VI) and Chromium(III) using a nickel modified screen printed carbon ink electrode. Electrochemical characteristics of nickel modified electrode as well voltammetric behavior f...

Gc protein (vitamin D-binding protein): Gc genotyping and GcMAF precursor activity.

PubMed

Nagasawa, Hideko; Uto, Yoshihiro; Sasaki, Hideyuki; Okamura, Natsuko; Murakami, Aya; Kubo, Shinichi; Kirk, Kenneth L; Hori, Hitoshi

2005-01-01

The Gc protein (human group-specific component (Gc), a vitamin D-binding protein or Gc globulin), has important physiological functions that include involvement in vitamin D transport and storage, scavenging of extracellular G-actin, enhancement of the chemotactic activity of C5a for neutrophils in inflammation and macrophage activation (mediated by a GalNAc-modified Gc protein (GcMAF)). In this review, the structure and function of the Gc protein is focused on especially with regard to Gc genotyping and GcMAF precursor activity. A discussion of the research strategy "GcMAF as a target for drug discovery" is included, based on our own research.

Electrochemical detection of dopamine in the presence of ascorbic acid using graphene modified electrodes.

PubMed

Kim, Yang-Rae; Bong, Sungyool; Kang, Yeon-Joo; Yang, Yongtak; Mahajan, Rakesh Kumar; Kim, Jong Seung; Kim, Hasuck

2010-06-15

Dopamine plays a significant role in the function of human metabolism. It is important to develop sensitive sensor for the determination of dopamine without the interference by ascorbic acid. This paper reports the synthesis of graphene using a modified Hummer's method and its application for the electrochemical detection of dopamine. Electrochemical measurements were performed at glassy carbon electrode modified with graphene via drop-casting method. Cyclic voltammogram of ferri/ferrocyanide redox couple at graphene modified electrode showed an increased current intensity compared with glassy carbon electrode and graphite modified electrode. The decrease of charge transfer resistance was also analyzed by electrochemical impedance spectroscopy. The capacity of graphene modified electrode for selective detection of dopamine was confirmed in a sufficient amount of ascorbic acid (1 mM). The observed linear range for the determination of dopamine concentration was from 4 microM to 100 microM. The detection limit was estimated to be 2.64 microM. Copyright 2010 Elsevier B.V. All rights reserved.

Formation of g-C3N4@Ni(OH)2 Honeycomb Nanostructure and Asymmetric Supercapacitor with High Energy and Power Density.

PubMed

Dong, Bitao; Li, Mingyan; Chen, Sheng; Ding, Dawei; Wei, Wei; Gao, Guoxin; Ding, Shujiang

2017-05-31

Nickel hydroxide (Ni(OH) 2 ) has been regarded as a potential next-generation electrode material for supercapacitor owing to its attractive high theoretical capacitance. However, practical application of Ni(OH) 2 is hindered by its lower cycling life. To overcome the inherent defects, herein we demonstrate a unique interconnected honeycomb structure of g-C 3 N 4 and Ni(OH) 2 synthesized by an environmentally friendly one-step method. In this work, g-C 3 N 4 has excellent chemical stability and supports a perpendicular charge-transporting direction in charge-discharge process, facilitating electron transportation along that direction. The as-prepared composite exhibits higher specific capacities (1768.7 F g -1 at 7 A g -1 and 2667 F g -1 at 3 mV s -1 , respectively) compared to Ni(OH) 2 aggregations (968.9 F g -1 at 7 A g -1 ) and g-C 3 N 4 (416.5 F g -1 at 7 A g -1 ), as well as better cycling performance (∼84% retentions after 4000 cycles). As asymmetric supercapacitor, g-C 3 N 4 @Ni(OH) 2 //graphene exhibits high capacitance (51 F g -1 ) and long cycle life (72% retentions after 8000 cycles). Moreover, high energy density of 43.1 Wh kg -1 and power density of 9126 W kg -1 has been achieved. This attractive performance reveals that g-C 3 N 4 @Ni(OH) 2 with honeycomb architecture could find potential application as an electrode material for high-performance supercapacitors.

A Palladium-Tin Modified Microband Electrode Array for Nitrate Determination

PubMed Central

Fu, Yexiang; Bian, Chao; Kuang, Jian; Wang, Jinfen; Tong, Jianhua; Xia, Shanhong

2015-01-01

A microband electrode array modified with palladium-tin bimetallic composite has been developed for nitrate determination. The microband electrode array was fabricated by Micro Electro-Mechanical System (MEMS) technique. Palladium and tin were electrodeposited successively on the electrode, forming a double-layer structure. The effect of the Pd-Sn composite was investigated and its enhancement of catalytic activity and lifetime was revealed. The Pd-Sn modified electrode showed good linearity (R2 = 0.998) from 1 mg/L to 20 mg/L for nitrate determination with a sensitivity of 398 μA/(mg∙L−1∙cm2). The electrode exhibited a satisfying analytical performance after 60 days of storage, indicating a long lifetime. Good repeatability was also displayed by the Pd-Sn modified electrodes. The results provided an option for nitrate determination in water. PMID:26389904

Stabilization of electrogenerated copper species on electrodes modified with quantum dots.

PubMed

Martín-Yerga, Daniel; Costa-García, Agustín

2017-02-15

Quantum dots (QDs) have special optical, surface, and electronic properties that make them useful for electrochemical applications. In this work, the electrochemical behavior of copper in ammonia medium is described using bare screen-printed carbon electrodes and the same modified with CdSe/ZnS QDs. At the bare electrodes, the electrogenerated Cu(i) and Cu(0) species are oxidized by dissolved oxygen in a fast coupled chemical reaction, while at the QDs-modified electrode, the re-oxidation of Cu(i) and Cu(0) species can be observed, which indicates that they are stabilized by the nanocrystals present on the electrode surface. A weak adsorption is proposed as the main cause for this stabilization. The electrodeposition on electrodes modified with QDs allows the generation of random nanostructures with copper nanoparticles, avoiding the preferential nucleation onto the most active electrode areas.

A Disposable Organophosphorus Pesticides Enzyme Biosensor Based on Magnetic Composite Nano-Particles Modified Screen Printed Carbon Electrode

PubMed Central

Gan, Ning; Yang, Xin; Xie, Donghua; Wu, Yuanzhao; Wen, Weigang

2010-01-01

A disposable organophosphorus pesticides (OPs) enzyme biosensor based on magnetic composite nanoparticle-modified screen printed carbon electrodes (SPCE) has been developed. Firstly, an acetylcholinesterase (AChE)-coated Fe3O4/Au (GMP) magnetic nanoparticulate (GMP-AChE) was synthesized. Then, GMP-AChE was absorbed on the surface of a SPCE modified by carbon nanotubes (CNTs)/nano-ZrO2/prussian blue (PB)/Nafion (Nf) composite membrane by an external magnetic field. Thus, the biosensor (SPCE│CNTs/ZrO2/PB/Nf│GMP-AChE) for OPs was fabricated. The surface of the biosensor was characterized by scanning electron micrography (SEM) and X-ray fluorescence spectrometery (XRFS) and its electrochemical properties were studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The degree of inhibition (A%) of the AChE by OPs was determined by measuring the reduction current of the PB generated by the AChE-catalyzed hydrolysis of acetylthiocholine (ATCh). In pH = 7.5 KNO3 solution, the A was related linearly to the concentration of dimethoate in the range from 1.0 × 10−3–10 ng·mL−1 with a detection limit of 5.6 × 10−4 ng·mL−1. The recovery rates in Chinese cabbage exhibited a range of 88%–105%. The results were consistent with the standard gas chromatography (GC) method. Compared with other enzyme biosensors the proposed biosensor exhibited high sensitivity, good selectivity with disposable, low consumption of sample. In particular its surface can be easily renewed by removal of the magnet. The convenient, fast and sensitive voltammetric measurement opens new opportunities for OPs analysis. PMID:22315558

Reduction-oxidation Enabled Glass-ceramics to Stainless Steel Bonding Part II interfacial bonding analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Steve Xunhu

2015-09-01

Among glass-ceramic compositions modified with a variety of oxidants (AgO, FeO, NiO, PbO, SnO, CuO, CoO, MoO 3 and WO 3) only CuO and CoO doped glass-ceramics showed existence of bonding oxides through reduction-oxidation (redox) at the GC-SS interface. The CuO-modified glass-ceramics demonstrate the formation of a continuous layer of strong bonding Cr 2O 3 at the interface in low partial oxygen (PO 2) atmosphere. However, in a local reducing atmosphere, the CuO is preferentially reduced at the surface of glass-ceramic rather than the GC-SS interface for redox. The CoO-modified glass-ceramics demonstrate improved GC-SS bonding. But the low mobility ofmore » Co ++ ions in the GC limited the amount of CoO that can diffuse to and participate in redox at the interface.« less

Investigation on direct electrochemical and electrocatalytic behavior of hemoglobin on palladium-graphene modified electrode.

PubMed

Chen, Wei; Niu, Xueliang; Li, Xiaoyan; Li, Xiaobao; Li, Guangjiu; He, Bolin; Li, Qiutong; Sun, Wei

2017-11-01

Palladium-graphene (Pd-GR) nanocomposite was acted as modifier for construction of the modified electrode with direct electrochemistry of hemoglobin (Hb) realized. By using Nafion as the immobilization film, Hb was fixed tightly on Pd-GR nanocomposite modified carbon ionic liquid electrode. Electrochemical behaviors of Hb modified electrode were checked by cyclic voltammetry and a pair of redox peaks originated from direct electron transfer of Hb was appeared. The Hb modified electrode had excellent electrocatalytic activity to the reduction of trichloroacetic acid and sodium nitrite in the concentration range from 0.6 to 13.0mmol·L -1 and from 0.04 to 0.5 mmol·L -1 . Therefore Pd-GR nanocomposite was proven to be a good candidate for the fabrication of third-generation electrochemical biosensor. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparation of hemoglobin-modified boron-doped diamond for acrylamide biosensors

NASA Astrophysics Data System (ADS)

Umam, K.; Saepudin, E.; Ivandini, T. A.

2017-04-01

Boron-doped diamond (BDD) electrode was modified with haemoglobin to develop electrochemical biosensors of acrylamide. Prior to modify with haemoglobin, the BDD was modified by gold nanoparticles to increase the affinity of BDD against haemoglobin. The electrochemical behaviour of the electrode in the presence of acrylamide was studied in comparison to haemoglobin-modified gold electrodes. Cyclic voltammetry indicated the optimum responses in 0.1 M sodium acetate buffer at pH 5. The responses were linear to the acrylamide concentration range of 5-50 μM with an estimated detection limit of 5.14 μM, suggesting that the electrode was promising for acrylamide biosensors.

Electrochemiluminescence of luminol at the titanate nanotubes modified glassy carbon electrode.

PubMed

Xu, Guifang; Zeng, Xiaoxue; Lu, Shuangyan; Dai, Hong; Gong, Lingshan; Lin, Yanyu; Wang, Qingping; Tong, Yuejin; Chen, Guonan

2013-01-01

A new strategy for the construction of a sensitive and stable electrochemiluminescent platform based on titanate nanotubes (TNTs) and Nafion composite modified electrode for luminol is described, TNTs contained composite modified electrodes that showed some photocatalytic activity toward luminol electrochemiluminescence emission, and thus could dramatically enhance luminol light emission. This extremely sensitive and stable platform allowed a decrease of the experiment electrochemiluminescence luminol reagent. In addition, in luminol solution at low concentrations, we compared the capabilities of a bare glassy carbon electrode with the TNT composite modified electrode for hydrogen peroxide detection. The results indicated that compared with glassy carbon electrode this platform was extraordinarily sensitive to hydrogen peroxide. Therefore, by combining with an appropriate enzymatic reaction, this platform would be a sensitive matrix for many biomolecules.

Imprinted zeolite modified carbon paste electrode as a potentiometric sensor for uric acid

NASA Astrophysics Data System (ADS)

Khasanah, Miratul; Widati, Alfa Akustia; Fitri, Sarita Aulia

2016-03-01

Imprinted zeolite modified carbon paste electrode (carbon paste-IZ) has been developed and applied to determine uric acid by potentiometry. The imprinted zeolite (IZ) was synthesized by the mole ratio of uric acid/Si of 0.0306. The modified electrode was manufactured by mass ratio of carbon, IZ and solid paraffin was 40:25:35. The modified electrode had shown the measurement range of 10-5 M to 10-2 M with Nernst factor of 28.6 mV/decade, the detection limit of 5.86 × 10-6 M and the accuracy of 95.3 - 105.0%. Response time of the electrode for uric acid 10-5 M - 10-2 M was 25 - 44 s. The developed electrode showed the high selectivity toward uric acid in the urea matrix. Life time of the carbon paste-IZ electrode was 10 weeks.

Development of amperometric lysine biosensors based on Au nanoparticles/multiwalled carbon nanotubes/polymers modified Au electrodes.

PubMed

Chauhan, Nidhi; Singh, Anamika; Narang, Jagriti; Dahiya, Swati; Pundir, C S

2012-11-07

The construction of two amperometric l-lysine biosensors is described in this study. The construction comprises the covalent immobilization of lysine oxidase (LOx) onto nanocomposite composed of gold nanoparticles (AuNPs) and carboxylated multiwalled carbon nanotubes (c-MWCNT), decorated on (i) polyaniline (PANI) and (ii) poly 1,2 diaminobenzene (DAB), electrodeposited on Au electrodes. The biosensors were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and electrochemical impedance spectroscopy (EIS) studies. The optimum response (current) was observed within 2 s at pH 7.0 and 25 °C for LOx/AuNPs/c-MWCNT/PANI/Au, and 4 s at pH 7.0 and 30 °C for LOx/AuNPs/c-MWCNT/DAB/Au electrodes. There was a linear relationship between current and lysine concentration ranging from 5.0 to 600 μM for LOx/AuNPs/c-MWCNT/PANI/Au with a detection limit of 5.0 μM, and 20 to 600 μM for the LOx/AuNPs/c-MWCNT/DAB/Au electrode with a detection limit of 20 μM. The PANI modified electrode was in good agreement with the standard HPLC method, with a better correlation (r = 0.992) compared to the DAB modified electrode (r = 0.986). These observations revealed that the PANI modified Au electrode was better than the DAB modified electrode, and hence it was employed for the determination of lysine in milk, pharmaceutical tablets and sera. The PANI modified electrode showed a half life of 120 days, compared to that of 90 days for the DAB modified electrode, after their 100 uses, when stored at 4 °C.

Electrochemical and in situ spectroscopic studies of materials of relevance to energy storage and electrocatalysis

NASA Astrophysics Data System (ADS)

Mo, Yibo

In situ X-ray absorption (XAS), surface enhanced Raman spectroscopy (SERS) and rotating ring disk electrode techniques have been employed for the characterization of materials of relevance to electrochemical energy storage and electrocatalysis. In particular, analysis of in situ Ir LIII-edge extended X-ray absorption fine structure (EXAFS) of IrO2 films electrodeposited on Au substrates yielded Ir-O bond lengths decreasing in the sequence 2.02, 1.97 and 1.93 A, for Ir3+, Ir4+ and Ir5+ sites, respectively. Although features consistent with the presence of crystalline IrO2 in the highly hydrated films were found from in situ SERS, the lack of intense shells in the FT of the EXAFS function beyond the nearest oxygen neighbors indicates that the films by and large do not display long range order. In similar studies, the Fourier transform of the k3-weighted Ru K-edge EXAFS of electrodeposited RuO2 films recorded in situ were characterized by two shells attributed to Ru-O and Ru-Ru interactions at 1.94(1) and 3.12(2) A, in agreement with results obtained ex situ for Ru4+ in hydrous RuO2, whereas films in the reduced state yielded a single Ru-O interaction shell at 2.02(1) A. Extensions of these in situ XAS to the study of electrocatalysts for the nitrite reduction made it possible to identify and characterize the electronic and structural properties of a nitrosyl iron porphyrin adduct adsorbed on an electrode surface via the analysis of Fe K-edge XAS data. The effects of Se and S ad-atoms on the electrocatalytic activity of Pt electrodes have been examined using RRDE techniques. In acid, within a rather narrow range of coverages, both S- and Se-modified Pt surfaces promote the 2-electron reduction of dioxygen to hydrogen peroxide at ca. 100% faradaic efficiency over a wide potential region. Also developed were methods for immobilizing unsupported dispersed high area Pt particles a glassy carbon (GC) disk of a rotating Pt(ring)/GC(disk) electrode assembly allowing electrochemical measurements to be performed under forced convection with only minimal losses of Pt from the surface.

Evaluating brain-computer interface performance using color in the P300 checkerboard speller.

PubMed

Ryan, D B; Townsend, G; Gates, N A; Colwell, K; Sellers, E W

2017-10-01

Current Brain-Computer Interface (BCI) systems typically flash an array of items from grey to white (GW). The objective of this study was to evaluate BCI performance using uniquely colored stimuli. In addition to the GW stimuli, the current study tested two types of color stimuli (grey to color [GC] and color intensification [CI]). The main hypotheses were that in a checkboard paradigm, unique color stimuli will: (1) increase BCI performance over the standard GW paradigm; (2) elicit larger event-related potentials (ERPs); and, (3) improve offline performance with an electrode selection algorithm (i.e., Jumpwise). Online results (n=36) showed that GC provides higher accuracy and information transfer rate than the CI and GW conditions. Waveform analysis showed that GC produced higher amplitude ERPs than CI and GW. Information transfer rate was improved by the Jumpwise-selected channel locations in all conditions. Unique color stimuli (GC) improved BCI performance and enhanced ERPs. Jumpwise-selected electrode locations improved offline performance. These results show that in a checkerboard paradigm, unique color stimuli increase BCI performance, are preferred by participants, and are important to the design of end-user applications; thus, could lead to an increase in end-user performance and acceptance of BCI technology. Copyright © 2017 International Federation of Clinical Neurophysiology. All rights reserved.

Application of three-dimensional reduced graphene oxide-gold composite modified electrode for direct electrochemistry and electrocatalysis of myoglobin.

PubMed

Shi, Fan; Xi, Jingwen; Hou, Fei; Han, Lin; Li, Guangjiu; Gong, Shixing; Chen, Chanxing; Sun, Wei

2016-01-01

In this paper a three-dimensional (3D) reduced graphene oxide (RGO) and gold (Au) composite was synthesized by electrodeposition and used for the electrode modification with carbon ionic liquid electrode (CILE) as the substrate electrode. Myoglobin (Mb) was further immobilized on the surface of 3D RGO-Au/CILE to obtain an electrochemical sensing platform. Direct electrochemistry of Mb on the modified electrode was investigated with a pair of well-defined redox waves appeared on cyclic voltammogram, indicating the realization of direct electron transfer of Mb with the modified electrode. The results can be ascribed to the presence of highly conductive 3D RGO-Au composite on the electrode surface that accelerate the electron transfer rate between the electroactive center of Mb and the electrode. The Mb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid in the concentration range from 0.2 to 36.0 mmol/L with the detection limit of 0.06 mmol/L (3σ). Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis of ZnO nanorods and their application in the construction of a nanostructure-based electrochemical sensor for determination of levodopa in the presence of carbidopa.

PubMed

Molaakbari, Elahe; Mostafavi, Ali; Beitollahi, Hadi; Alizadeh, Reza

2014-09-07

A novel carbon paste electrode modified with ZnO nanorods and 5-(4'-amino-3'-hydroxy-biphenyl-4-yl)-acrylic acid (3,4'-AAZCPE) was fabricated. The electrochemical study of the modified electrode, as well as its efficiency for the electrocatalytic oxidation of levodopa, is described. The electrode was employed to study the electrocatalytic oxidation of levodopa, using cyclic voltammetry (CV), chronoamperometry (CHA), and square-wave voltammetry (SWV) as diagnostic techniques. It has been found that the oxidation of levodopa at the surface of the modified electrode occurs at a potential of about 370 mV less positive than that of an unmodified carbon paste electrode. The SWV results exhibit a linear dynamic range from 1.0 × 10(-7) M to 7.0 × 10(-5) M and a detection limit of 3.5 × 10(-8) M for levodopa. In addition, this modified electrode was used for the simultaneous determination of levodopa and carbidopa. Finally, the modified electrode was used for the determination of levodopa and carbidopa in some real samples.

Electrochemical investigation of the voltammetric determination of hydrochlorothiazide using a nickel hydroxide modified nickel electrode.

PubMed

Machini, Wesley B S; David-Parra, Diego N; Teixeira, Marcos F S

2015-12-01

The preparation and electrochemical characterization of a nickel hydroxide modified nickel electrode as well as its behavior as electrocatalyst toward the oxidation of hydrochlorothiazide (HCTZ) were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of HCTZ were explored using cyclic voltammetry. The voltammetric response of the modified electrode in the detection of HCTZ is based on the electrochemical oxidation of the Ni(II)/Ni(III) and a chemical redox process. The analytical parameters for the electrooxidation of HCTZ by the nickel hydroxide modified nickel electrode were obtained in NaOH solution, in which the linear voltammetric response was in the concentration range from 1.39×10(-5) to 1.67×10(-4)mol L(-1) with a limit of detection of 7.92×10(-6)mol L(-1) and a sensitivity of 0.138 μA Lmmol(-1). Tafel analysis was used to elucidate the kinetics and mechanism of HCTZ oxidation by the modified electrode. Copyright © 2015 Elsevier B.V. All rights reserved.

One-Step Electrochemical Fabrication of Reduced Graphene Oxide/Gold Nanoparticles Nanocomposite-Modified Electrode for Simultaneous Detection of Dopamine, Ascorbic Acid, and Uric Acid

PubMed Central

Lee, Chang-Seuk; Yu, Su Hwan; Kim, Tae Hyun

2017-01-01

Here, we introduce the preparation of the hybrid nanocomposite-modified electrode consisting of reduced graphene oxide (RGO) and gold nanoparticles (AuNPs) using the one-step electrochemical method, allowing for the simultaneous and individual detection of dopamine (DA), ascorbic acid (AA), and uric acid (UA). RGO/AuNPs nanocomposite was formed on a glassy carbon electrode by the co-reduction of GO and Au3+ using the potentiodynamic method. The RGO/AuNPs nanocomposite-modified electrode was produced by subjecting a mixed solution of GO and Au3+ to cyclic sweeping from −1.5 V to 0.8 V (vs. Ag/AgCl) at a scan rate 10 mV/s for 3 cycles. The modified electrode was characterized by scanning electron microscopy, Raman spectroscopy, contact angle measurement, electrochemical impedance spectroscopy, and cyclic voltammetry. Voltammetry results confirm that the RGO/AuNPs nanocomposite-modified electrode has high catalytic activity and good resolution for the detection of DA, AA, and UA. The RGO/AuNPs nanocomposite-modified electrode exhibits stable amperometric responses for DA, AA, and UA, respectively, and its detection limits were estimated to be 0.14, 9.5, and 25 μM. The modified electrode shows high selectivity towards the determination of DA, AA, or UA in the presence of potentially active bioelements. In addition, the resulting sensor exhibits many advantages such as fast amperometric response, excellent operational stability, and appropriate practicality. PMID:29301209

Efficient inverted polymer solar cells based on conjugated polyelectrolyte and zinc oxide modified ITO electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Tao; Zhu, Xiaoguang; Tu, Guoli, E-mail: tgl@hust.edu.cn

Efficient inverted polymer solar cells (PSCs) were constructed by utilizing a conjugated polyelectrolyte PF{sub EO}SO{sub 3}Na and zinc oxide to modify the indium tin oxide (ITO) electrode. The ITO electrode modified by PF{sub EO}SO{sub 3}Na and zinc oxide possesses high transparency, increased electron mobility, smoothened surface, and lower work function. PTB7:PC{sub 71}BM inverted PSCs containing the modified ITO electrode achieved a high power conversion efficiency (PCE) of 8.49%, exceeding that of the control device containing a ZnO modified ITO electrode (7.48%). Especially, PCE-10:PC{sub 71}BM inverted polymer solar cells achieved a high PCE up to 9.4%. These results demonstrate a usefulmore » approach to improve the performance of inverted polymer solar cells.« less

Application of N-doped graphene modified carbon ionic liquid electrode for direct electrochemistry of hemoglobin.

PubMed

Sun, Wei; Dong, Lifeng; Deng, Ying; Yu, Jianhua; Wang, Wencheng; Zhu, Qianqian

2014-06-01

Nitrogen-doped graphene (NG) was synthesized and used for the investigation on direct electrochemistry of hemoglobin (Hb) with a carbon ionic liquid electrode as the substrate electrode. Due to specific characteristics of NG such as excellent electrocatalytic property and large surface area, direct electron transfer of Hb was realized with enhanced electrochemical responses appearing. Electrochemical behaviors of Hb on the NG modified electrode were carefully investigated with the electrochemical parameters calculated. The Hb modified electrode exhibited excellent electrocatalytic reduction activity toward different substrates, such as trichloroacetic acid and H2O2, with wider dynamic range and lower detection limit. These findings show that NG can be used for the preparation of chemically modified electrodes with improved performance and has potential applications in electrochemical sensing. Copyright © 2014 Elsevier B.V. All rights reserved.

Pristine multi-walled carbon nanotubes/SDS modified carbon paste electrode as an amperometric sensor for epinephrine.

PubMed

Thomas, Tony; Mascarenhas, Ronald J; D' Souza, Ozma J; Detriche, Simon; Mekhalif, Zineb; Martis, Praveen

2014-07-01

An amperometric sensor for the determination of epinephrine (EP) was fabricated by modifying the carbon paste electrode (CPE) with pristine multi-walled carbon nanotubes (pMWCNTs) using bulk modification followed by drop casting of sodium dodecyl sulfate (SDS) onto the surface for its optimal potential application. The modified electrode showed an excellent electrocatalytic activity towards EP by decreasing the overpotential and greatly enhancing the current sensitivity. FE-SEM images confirmed the dispersion of pMWCNTs in the CPE matrix. EDX analysis ensured the surface coverage of SDS. A comparative study of pMWCNTs with those of oxidized MWCNTs (MWCNTsOX) modified electrodes reveals that the former is the best base material for the construction of the sensor with advantages of lower oxidation overpotential and the least background current. The performance of the modified electrode was impressive in terms of the least charge transfer resistance (Rct), highest values for diffusion coefficient (DEP) and standard heterogeneous electron transfer rate constant (k°). Analytical characterization of the modified electrode exhibited two linear dynamic ranges from 1.0×10(-7) to 1.0×10(-6)M and 1.0×10(-6) to 1.0×10(-4)M with a detection limit of (4.5±0.18)×10(-8)M. A 100-fold excess of serotonin, acetaminophen, folic acid, uric acid, tryptophan, tyrosine and cysteine, 10-fold excess of ascorbic acid and twofold excess of dopamine do not interfere in the quantification of EP at this electrode. The analytical applications of the modified electrode were demonstrated by determining EP in spiked blood serum and adrenaline tartrate injection. The modified electrode involves a simple fabrication procedure, minimum usage of the modifier, quick response, excellent stability, reproducibility and anti-fouling effects. Copyright © 2014 Elsevier B.V. All rights reserved.

Chemically modified graphite for electrochemical cells

DOEpatents

Greinke, Ronald Alfred; Lewis, Irwin Charles

1998-01-01

This invention relates to chemically modified graphite particles: (a) that are useful in alkali metal-containing electrode of a electrochemical cell comprising: (i) the electrode, (ii) a non-aqueous electrolytic solution comprising an organic aprotic solvent which solvent tends to decompose when the electrochemical cell is in use, and an electrically conductive salt of an alkali metal, and (iii) a counterelectrode; and (b) that are chemically modified with fluorine, chlorine, iodine or phosphorus to reduce such decomposition. This invention also relates to electrodes comprising such chemically modified graphite and a binder and to electrochemical cells containing such electrodes.

Pd0@Polyoxometalate Nanostructures as Green Electrocatalysts: Illustrative Example of Hydrogen Production

PubMed Central

Biboum, Rosa N.; Keita, Bineta; Franger, Sylvain; Njiki, Charles P. Nanseu; Zhang, Guangjin; Zhang, Jie; Liu, Tianbo; Mbomekalle, Israel-Martyr; Nadjo, Louis

2010-01-01

Green-chemistry type procedures were used to synthesize Pd0 nanostructures encapsulated by a vanadium-substituted Wells-Dawson-type polyoxometalate (Pd0@POM). The cyclic voltammogram run with the Pd0@POM-modified glassy carbon electrode shows well-defined waves, associated with Pd0 nanostructures and the VV/VIV redox couple. The Pd0@POM-modified electrode displayed remarkably reproducible cyclic voltammetry patterns. The hydrogen evolution reaction (HER) was selected as an illustrative example to test the electrocatalytic behavior of the electrode. The kinetic parameters of the HER show the high efficiency of the Pd0@POM-modified electrode. This is the first example of electrochemical characterization of a modified electrode based on a vanado-tungstic POM and Pd0 nanostructures.

Cryogenic Collection of Complete Subsurface Samples for Molecular Biological Analysis

DTIC Science & Technology

2012-05-01

Nitrate was analyzed by ion chromatography ( Dionex IC25) and had a detection limit of 0.01 mg/L. Fluorescein was measured using a flow-through...dissolved oxygen (DO) with a flow through electrode, Nitrate by ion chromatography , and fluorescein with a flow through fluorometer. 1.9 LARGE...measured by headspace gas chromatography (HP 7694 Headspace Sampler attached to an HP 5890 GC with an FID detector). The GC method had a detection

Using sewage sludge pyrolytic gas to modify titanium alloy to obtain high-performance anodes in bio-electrochemical systems

NASA Astrophysics Data System (ADS)

Gu, Yuan; Ying, Kang; Shen, Dongsheng; Huang, Lijie; Ying, Xianbin; Huang, Haoqian; Cheng, Kun; Chen, Jiazheng; Zhou, Yuyang; Chen, Ting; Feng, Huajun

2017-12-01

Titanium is under consideration as a potential stable bio-anode because of its high conductivity, suitable mechanical properties, and electrochemical inertness in the operating potential window of bio-electrochemical systems; however, its application is limited by its poor electron-transfer capacity with electroactive bacteria and weak ability to form biofilms on its hydrophobic surface. This study reports an effective and low-cost way to convert a hydrophobic titanium alloy surface into a hydrophilic surface that can be used as a bio-electrode with higher electron-transfer rates. Pyrolytic gas of sewage sludge is used to modify the titanium alloy. The current generation, anodic biofilm formation surface, and hydrophobicity are systematically investigated by comparing bare electrodes with three modified electrodes. Maximum current density (15.80 A/m2), achieved using a modified electrode, is 316-fold higher than that of the bare titanium alloy electrode (0.05 A/m2) and that achieved by titanium alloy electrodes modified by other methods (12.70 A/m2). The pyrolytic gas-modified titanium alloy electrode can be used as a high-performance and scalable bio-anode for bio-electrochemical systems because of its high electron-transfer rates, hydrophilic nature, and ability to achieve high current density.

Electrocatalytic response of poly(cobalt tetraaminophthalocyanine)/multi-walled carbon nanotubes-Nafion modified electrode toward sulfadiazine in urine*

PubMed Central

Hong, Xiao-ping; Zhu, Yan; Zhang, Yan-zhen

2012-01-01

A highly sensitive amperometric sulfadiazine sensor fabricated by electrochemical deposition of poly(cobalt tetraaminophthalocyanine) (poly(CoIITAPc)) on the surface of a multi-walled carbon nanotubes-Nafion (MWCNTs-Nafion) modified electrode is described. This electrode showed a very attractive performance by combining the advantages of CoIITAPc, MWCNTs, and Nafion. Compared with the bare glassy carbon electrode (GCE) and the MWCNTs-Nafion modified electrode, the electrocatalytic activity of poly(CoIITAPc)-coated MWCNTs-Nafion GCE generated greatly improved electrochemical detections toward sulfadiazine including low oxidation potential, high current responses, and good anti-fouling performance. The oxidation peak currents of sulfadiazine obtained on the new modified electrode increased linearly while increasing the concentration of sulfadiazine from 0.5 to 43.5 μmol/L with the detection limit of 0.17 μmol/L. PMID:22661213

Correlation of the impedance and effective electrode area of doped PEDOT modified electrodes for brain-machine interfaces.

PubMed

Harris, Alexander R; Molino, Paul J; Kapsa, Robert M I; Clark, Graeme M; Paolini, Antonio G; Wallace, Gordon G

2015-05-07

Electrode impedance is used to assess the thermal noise and signal-to-noise ratio for brain-machine interfaces. An intermediate frequency of 1 kHz is typically measured, although other frequencies may be better predictors of device performance. PEDOT-PSS, PEDOT-DBSA and PEDOT-pTs conducting polymer modified electrodes have reduced impedance at 1 kHz compared to bare metal electrodes, but have no correlation with the effective electrode area. Analytical solutions to impedance indicate that all low-intermediate frequencies can be used to compare the electrode area at a series RC circuit, typical of an ideal metal electrode in a conductive solution. More complex equivalent circuits can be used for the modified electrodes, with a simplified Randles circuit applied to PEDOT-PSS and PEDOT-pTs and a Randles circuit including a Warburg impedance element for PEDOT-DBSA at 0 V. The impedance and phase angle at low frequencies using both equivalent circuit models is dependent on the electrode area. Low frequencies may therefore provide better predictions of the thermal noise and signal-to-noise ratio at modified electrodes. The coefficient of variation of the PEDOT-pTs impedance at low frequencies was lower than the other conducting polymers, consistent with linear and steady-state electroactive area measurements. There are poor correlations between the impedance and the charge density as they are not ideal metal electrodes.

Voltammetric enzyme sensor for urea using mercaptohydroquinone-modified gold electrode as the base transducer.

PubMed

Mizutani, F; Yabuki, S; Sato, Y

1997-01-01

A voltammetric urea-sensing electrode was prepared by combining a lipid-attached urease layer with a 2,5-dihydroxythiophenol-modified gold electrode. A self-assembled monolayer of dihydroxythiophenol was prepared on the gold surface by soaking the electrode into an ethanolic solution containing the modifier. A layer of the lipid-attached enzyme and that of acetyl cellulose overcoat were successively made on the dihydroxythiophenol-modified electrode by applying a dip-coating procedure. The addition of urea in a test solution (10 mM phosphate buffer, pH 7.0) brought about an increase of pH near the urease layer. The pH shift accompanied a negative shift of the anodic peak, which corresponded to the electro-oxidation of dihydroxyphenol moiety to form quinone, on the linear sweep voltammograms for the urease/dihydroxythiophenol electrode. The concentration of urea (0.2-5 mM) could be determined by measuring the electrode current at -0.05 V versus Ag/AgCl from the voltammogram. The electrode was applied to the determination of urea in human urine; the measurement of electrode current at such a low potential provided the urea determination without any electrochemical interference from L-ascorbic acid and uric acid.

Direct and mediated electrochemistry of peroxidase and its electrocatalysis on a variety of screen-printed carbon electrodes: amperometric hydrogen peroxide and phenols biosensor.

PubMed

Chekin, Fereshteh; Gorton, Lo; Tapsobea, Issa

2015-01-01

This study compares the behaviour of direct and mediated electrochemistry of horseradish peroxidase (HRP) immobilised on screen-printed carbon electrodes (SPCEs), screen-printed carbon electrodes modified with carboxyl-functionalised multi-wall carbon nanotubes (MWCNT-SPCEs) and screen-printed carbon electrodes modified with carboxyl-functionalised single-wall carbon nanotubes (SWCNT-SPCEs). The techniques of cyclic voltammetry and amperometry in the flow mode were used to characterise the properties of the HRP immobilised on screen-printed electrodes. From measurements of the mediated and mediatorless currents of hydrogen peroxide reduction at the HRP-modified electrodes, it was concluded that the fraction of enzyme molecules in direct electron transfer (DET) contact with the electrode varies substantially for the different electrodes. It was observed that the screen-printed carbon electrodes modified with carbon nanotubes (MWCNT-SPCEs and SWCNT-SPCEs) demonstrated a substantially higher percentage (≈100 %) of HRP molecules in DET contact than the screen-printed carbon electrodes (≈60 %). The HRP-modified electrodes were used for determination of hydrogen peroxide in mediatorless mode. The SWCNT-SPCE gave the lowest detection limit (0.40 ± 0.09 μM) followed by MWCNT-SPCE (0.48 ± 0.07 μM) and SPCE (0.98 ± 0.2 μM). These modified electrodes were additionally developed for amperometric determination of phenolic compounds. It was found that the SWCNT-SPCE gave a detection limit for catechol of 110.2 ± 3.6 nM, dopamine of 640.2 ± 9.2 nM, octopamine of 3341 ± 15 nM, pyrogallol of 50.10 ± 2.9 nM and 3,4-dihydroxy-L-phenylalanine of 980.7 ± 8.7 nM using 50 μM H2O2 in the flow carrier.

Investigation on the charging process of Li 2O 2-based air electrodes in Li-O 2 batteries with organic carbonate electrolytes

NASA Astrophysics Data System (ADS)

Xu, Wu; Viswanathan, Vilayanur V.; Wang, Deyu; Towne, Silas A.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Zhang, Ji-Guang

The charging process of Li 2O 2-based air electrodes in Li-O 2 batteries with organic carbonate electrolytes was investigated using in situ gas chromatography/mass spectroscopy (GC/MS) to analyze gas evolution. A mixture of Li 2O 2/Fe 3O 4/Super P carbon/polyvinylidene fluoride (PVDF) was used as the starting air electrode material, and 1-M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in carbonate-based solvents was used as the electrolyte. We found that Li 2O 2 was actively reactive to 1-methyl-2-pyrrolidinone and PVDF that were used to prepare the electrode. During the first charging (up to 4.6 V), O 2 was the main component in the gases released. The amount of O 2 measured by GC/MS was consistent with the amount of Li 2O 2 that decomposed during the electrochemical process as measured by the charge capacity, which is indicative of the good chargeability of Li 2O 2. However, after the cell was discharged to 2.0 V in an O 2 atmosphere and then recharged to ∼4.6 V, CO 2 was dominant in the released gases. Further analysis of the discharged air electrodes by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy indicated that lithium-containing carbonate species (lithium alkyl carbonates and/or Li 2CO 3) were the main discharge products. Therefore, compatible electrolytes and electrodes, as well as the electrode-preparation procedures, need to be developed for rechargeable Li-air batteries for long term operation.

Application of a palladium hexacyanoferrate film-modified aluminum electrode to electrocatalytic oxidation of hydrazine.

PubMed

Razmi, Habib; Azadbakht, Azadeh; Sadr, Moayad Hossaini

2005-11-01

A palladium hexacyanoferrate (PdHCF) film as an electrocatalytic material was obtained at an aluminum (Al) electrode by a simple electroless dipping method. The modified Al electrode demonstrated a well-behaved redox couple due to the redox reaction of the PdHCF film. The PdHCF film showed an excellent electrocatalytic activity toward the oxidation of hydrazine. The electrocatalytic oxidation of hydrazine was studied by cyclic voltammetry and rotating disk electrode voltammetry techniques. A calibration graph obtained for the hydrazine consisted of two segments (localized at concentration ranges 0.39-10 and 20-75 mM). The rate constant k and transfer coefficient alpha for the catalytic reaction and the diffusion coefficient of hydrazine in the solution D, were found to be 3.11 x 10(3) M(-1) s(-1), 0.52 and 8.03 x 10(-6) cm2 s(-1) respectively. The modified electrode was used to amperometric determination of hydrazine in photographic developer. The interference of ascorbic acid and thiosulfate were investigated and greatly reduced using a thin film of Nafion on the modified electrode. The modified electrode indicated reproducible behavior and a high level of stability during electrochemical experiments, making it particularly suitable for analytical purposes.

Highly sensitive and selective detection of dopamine based on hollow gold nanoparticles-graphene nanocomposite modified electrode.

PubMed

Zhu, Wencai; Chen, Ting; Ma, Xuemei; Ma, Houyi; Chen, Shenhao

2013-11-01

Highly dispersed hollow gold-graphene (HAu-G) nanocomposites were synthesized by a two-step method. The immobilization of hollow gold nanoparticles (HAu NPs) onto the surface of graphene sheets was achieved by mixing an aqueous solution of HAu NPs with a poly(N-vinylpyrrolidone)-functionalized graphene dispersion at room temperature. A glassy carbon electrode (GCE) was modified with the nanocomposites, and the as-prepared modified electrode displayed high electrocatalytic activity and extraordinary electronic transport properties. Amperometric detection of dopamine (DA) performed with the HAu-G modified electrode exhibits a good linearity between 0.08 and 600 μM with a low detection limit of 0.05 μM (S/N=3) and also possesses good reproducibility and operational stability. The interference of ascorbic acid (AA) and uric acid (UA) can be excluded when using differential pulse voltammetric technique. In addition, this type of modified electrode can also be applied to the determination of DA content in dopamine hydrochloride injection. It is obvious that the HAu-G modified electrode provides a new way to detect dopamine sensitively and selectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Development of electrochemical sensor for the determination of palladium ions (Pd2+) using flexible screen printed un-modified carbon electrode.

PubMed

Velmurugan, Murugan; Thirumalraj, Balamurugan; Chen, Shen-Ming; Al-Hemaid, Fahad M A; Ajmal Ali, M; Elshikh, Mohamed S

2017-01-01

To date, the development of different modified electrodes have received much attention in electrochemistry. The modified electrodes have some drawbacks such as high cost, difficult to handle and not eco friendly. Hence, we report an electrochemical sensor for the determination of palladium ions (Pd 2+ ) using an un-modified screen printed carbon electrode has been developed for the first time, which are characterized and studied via scanning electron microscope and cyclic voltammetry. Prior to determination of Pd 2+ ions, the operational conditions of un-modified SPCE was optimized using cyclic voltammetry and showed excellent electro-analytical behavior towards the determination of Pd 2+ ions. Electrochemical determination of Pd 2+ ions reveal that the un-modified electrode showed lower detection limit of 1.32μM with a linear ranging from 3 to 133.35μM towards the Pd 2+ ions concentration via differential pulse voltammetry. The developed sensor also applied to the successfully determination of trace level Pd 2+ ions in spiked water samples. In addition, the advantage of this type of electrode is simple, disposable and cost effective in electrochemical sensors. Copyright © 2016 Elsevier Inc. All rights reserved.

Fabrication of an Electrochemical Sensor Based on Gold Nanoparticles/Carbon Nanotubes as Nanocomposite Materials: Determination of Myricetin in Some Drinks

PubMed Central

Hajian, Reza; Yusof, Nor Azah; Faragi, Tayebe; Shams, Nafiseh

2014-01-01

In this paper, the electrochemical behavior of myricetin on a gold nanoparticle/ethylenediamine/multi-walled carbon-nanotube modified glassy carbon electrode (AuNPs/en/MWCNTs/GCE) has been investigated. Myricetin effectively accumulated on the AuNPs/en/MWCNTs/GCE and caused a pair of irreversible redox peaks at around 0.408 V and 0.191 V (vs. Ag/AgCl) in 0.1 mol L−1 phosphate buffer solution (pH 3.5) for oxidation and reduction reactions respectively. The heights of the redox peaks were significantly higher on AuNPs/en/MWNTs/GCE compare with MWCNTs/GC and there was no peak on bare GC. The electron-transfer reaction for myricetin on the surface of electrochemical sensor was controlled by adsorption. Some parameters including pH, accumulation potential, accumulation time and scan rate have been optimized. Under the optimum conditions, anodic peak current was proportional to myricetin concentration in the dynamic range of 5.0×10−8 to 4.0×10−5 mol L−1 with the detection limit of 1.2×10−8 mol L−1. The proposed method was successfully used for the determination of myricetin content in tea and fruit juices. PMID:24809346

Development of Novel Potentiometric Sensors for Determination of Lidocaine Hydrochloride in Pharmaceutical Preparations, Serum and Urine Samples

PubMed Central

Ali, Tamer Awad; Mohamed, Gehad Genidy; Yahya, Ghada A.

2017-01-01

This article is focused on the determination of lidocaine hydrochloride as a local anaesthetic drug. A potentiometric method based on modified screen-printed and modified carbon paste ion-selective electrodes was described for the determination of lidocaine hydrochloride in different pharmaceutical preparations and biological fluids (urine and serum). It was based on potentiometric titration of lidocaine hydrochloride using modified screen-printed and carbon paste electrodes as end point indicator sensors. The influences of the paste composition, different conditioning parameters and foreign ions on the electrodes performance were investigated and response times of the electrodes were studied. The electrodes showed Nernstian response of 58.9 and 57.5 mV decade-1 in the concentration range of 1×10-7–1×10-2 and 6.2×10-7–1×10-2 mol L-1 for modified screen-printed and carbon paste electrodes, respectively. The electrodes were found to be usable within the pH range of 2.0–8.0 and 2.0-7.5, exhibited a fast response time (about 6 and 4) low detection limit (1×10-7 and 6.2×10-7 mol L-1), long lifetime (6 and 4 months) and good stability for modified screen-printed (Electrode VII) and carbon paste electrodes (Electrode III), respectively. The electrodes were successfully applied for the determination of lidocaine hydrochloride in pure solutions, pharmaceutical preparation and biological fluids (urine and serum) samples. The results obtained applying these potentiometric electrodes were comparable with British pharmacopeia. The method validation parameters were optimized and the method can be applied for routine analysis of lidocaine hydrochloride drug. PMID:28979305

Development of Novel Potentiometric Sensors for Determination of Lidocaine Hydrochloride in Pharmaceutical Preparations, Serum and Urine Samples.

PubMed

Ali, Tamer Awad; Mohamed, Gehad Genidy; Yahya, Ghada A

2017-01-01

This article is focused on the determination of lidocaine hydrochloride as a local anaesthetic drug. A potentiometric method based on modified screen-printed and modified carbon paste ion-selective electrodes was described for the determination of lidocaine hydrochloride in different pharmaceutical preparations and biological fluids (urine and serum). It was based on potentiometric titration of lidocaine hydrochloride using modified screen-printed and carbon paste electrodes as end point indicator sensors. The influences of the paste composition, different conditioning parameters and foreign ions on the electrodes performance were investigated and response times of the electrodes were studied. The electrodes showed Nernstian response of 58.9 and 57.5 mV decade -1 in the concentration range of 1×10 -7 -1×10 -2 and 6.2×10 -7 -1×10 -2 mol L -1 for modified screen-printed and carbon paste electrodes, respectively. The electrodes were found to be usable within the pH range of 2.0-8.0 and 2.0-7.5, exhibited a fast response time (about 6 and 4) low detection limit (1×10 -7 and 6.2×10 -7 mol L -1 ), long lifetime (6 and 4 months) and good stability for modified screen-printed (Electrode VII) and carbon paste electrodes (Electrode III), respectively. The electrodes were successfully applied for the determination of lidocaine hydrochloride in pure solutions, pharmaceutical preparation and biological fluids (urine and serum) samples. The results obtained applying these potentiometric electrodes were comparable with British pharmacopeia. The method validation parameters were optimized and the method can be applied for routine analysis of lidocaine hydrochloride drug.

Synthesis of molecular imprinted polymer modified TiO{sub 2} nanotube array electrode and their photoelectrocatalytic activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu Na; Chen Shuo; Wang Hongtao

2008-10-15

A tetracycline hydrochloride (TC) molecularly imprinted polymer (MIP) modified TiO{sub 2} nanotube array electrode was prepared via surface molecular imprinting. Its surface was structured with surface voids and the nanotubes were open at top end with an average diameter of approximately 50 nm. The MIP-modified TiO{sub 2} nanotube array with anatase phase was identified by XRD and a distinguishable red shift in the absorption spectrum was observed. The MIP-modified electrode also exhibited a high adsorption capacity for TC due to its high surface area providing imprinted sites. Photocurrent was generated on the MIP-modified photoanode using the simulated solar spectrum andmore » increased with the increase of positive bias potential. Under simulated solar light irradiation, the MIP-modified TiO{sub 2} nanotube array electrode exhibited enhanced photoelectrocatalytic (PEC) activity with the apparent first-order rate constant being 1.2-fold of that with TiO{sub 2} nanotube array electrode. The effect of the thickness of the MIP layer on the PEC activity was also evaluated. - Graphical abstract: A tetracycline hydrochloride molecularly imprinted polymer modified TiO{sub 2} nanotube array electrode was prepared via surface molecular imprinting. It showed improved response to simulated solar light and higher adsorption capability for tetracycline hydrochloride, thereby exhibiting increased PEC activity under simulated solar light irradiation. The apparent first-order rate constant was 1.2-fold of that on TiO{sub 2} nanotube array electrode.« less

Molecularly imprinted electrochemical biosensor based on Fe@Au nanoparticles involved in 2-aminoethanethiol functionalized multi-walled carbon nanotubes for sensitive determination of cefexime in human plasma.

PubMed

Yola, Mehmet Lütfi; Eren, Tanju; Atar, Necip

2014-10-15

The molecular imprinting technique depends on the molecular recognition. It is a polymerization method around the target molecule. Hence, this technique creates specific cavities in the cross-linked polymeric matrices. In present study, a sensitive imprinted electrochemical biosensor based on Fe@Au nanoparticles (Fe@AuNPs) involved in 2-aminoethanethiol (2-AET) functionalized multi-walled carbon nanotubes (f-MWCNs) modified glassy carbon (GC) electrode was developed for determination of cefexime (CEF). The results of X-ray photoelectron spectroscopy (XPS) and reflection-absorption infrared spectroscopy (RAIRS) confirmed the formation of the developed surfaces. CEF imprinted film was constructed by cyclic voltammetry (CV) for 9 cycles in the presence of 80 mM pyrrole in phosphate buffer solution (pH 6.0) containing 20mM CEF. The developed electrochemical biosensor was validated according to the International Conference on Harmonisation (ICH) guideline and found to be linear, sensitive, selective, precise and accurate. The linearity range and the detection limit were obtained as 1.0 × 10(-10)-1.0 × 10(-8)M and 2.2 × 10(-11)M, respectively. The developed CEF imprinted sensor was successfully applied to real samples such as human plasma. In addition, the stability and reproducibility of the prepared molecular imprinted electrode were investigated. The excellent long-term stability and reproducibility of the prepared CEF imprinted electrodes make them attractive in electrochemical sensors. Copyright © 2014 Elsevier B.V. All rights reserved.

New β-Cyclodextrin Entrapped in Polyethyleneimine Film-Modified Electrodes for Pharmaceutical Compounds Determination

PubMed Central

Fritea, Luminţa; Tertiş, Mihaela; Cristea, Cecilia; Săndulescu, Robert

2013-01-01

The electrochemical behavior of ascorbic acid and uric acid on glassy carbon bare electrodes and ones modified with β-cyclodextrin entrapped in polyethyleneimine film has been investigated using square wave voltammetry. The electrode modification was achieved in order to separate the voltammetric peaks of ascorbic acid and uric acid when present in the same solution. On the modified electrodes the potential of the oxidation peak of the ascorbic acid was shifted to more negative values by over 0.3 V, while in the case of uric acid, the negative potential shift was about 0.15 V compared to the bare glassy carbon electrode. When the two compounds were found together in the solution, on the bare electrode only a single broad signal was observed, while on the modified electrode the peak potentials of these two compounds were separated by 0.4 V. When the uric acid concentration remained constant, the peak intensity of the ascorbic acid is increased linearly with the concentration (r2 = 0.996) and when the ascorbic acid concentration remains constant, the peak intensity of the uric acid increased linearly with the concentration (r2 = 0.992). FTIR measurements supported the formation of inclusion complexes. In order to characterize the modification of the electrodes microscopic studies were performed. The modified electrodes were successfully employed for the determination of ascorbic acid in pharmaceutical formulations with a detection limit of 0.22 μM. PMID:24287544

Green electrochemical modification of RVC foam electrode and improved H2O2 electrogeneration by applying pulsed current for pollutant removal.

PubMed

Zhou, Wei; Ding, Yani; Gao, Jihui; Kou, Kaikai; Wang, Yan; Meng, Xiaoxiao; Wu, Shaohua; Qin, Yukun

2018-02-01

The performance of cathode on H 2 O 2 electrogeneration is a critical factor that limits the practical application of electro-Fenton (EF) process. Herein, we report a simple but effective electrochemical modification of reticulated vitreous carbon foam (RVC foam) electrode for enhanced H 2 O 2 electrogeneration. Cyclic voltammetry, chronoamperometry, and X-ray photoelectron spectrum were used to characterize the modified electrode. Oxygen-containing groups (72.5-184.0 μmol/g) were introduced to RVC foam surface, thus resulting in a 59.8-258.2% higher H 2 O 2 yield. The modified electrodes showed much higher electrocatalytic activity toward O 2 reduction and good stability. Moreover, aimed at weakening the extent of electroreduction of H 2 O 2 in porous RVC foam, the strategy of pulsed current was proposed. H 2 O 2 concentration was 582.3 and 114.0% higher than the unmodified and modified electrodes, respectively. To test the feasibility of modification, as well as pulsed current, EF process was operated for removal of Reactive Blue 19 (RB19). The fluorescence intensity of hydroxybenzoic acid in EF with modified electrode is 3.2 times higher than EF with unmodified electrode, illustrating more hydroxyl radicals were generated. The removal efficiency of RB 19 in EF with unmodified electrode, modified electrode, and unmodified electrode assisted by pulsed current was 53.9, 68.9, and 81.1%, respectively, demonstrating that the green modification approach, as well as pulsed current, is applicable in EF system for pollutant removal. Graphical abstract ᅟ.

Green synthesis of nanosilver as a sensor for detection of hydrogen peroxide in water.

PubMed

Shukla, Vineet K; Yadav, Raghvendra S; Yadav, Poonam; Pandey, Avinash C

2012-04-30

Present "green" synthesis is an efficient, easy-going, fast, renewable, inexpensive, eco-friendly and non-toxic approach for nanosilver formation, which offers numerous benefits over physiochemical approaches. The X-ray diffraction (XRD) pattern suggests the formation and crystallinity of nanosilver. The average particle size of silver nanoparticles was 8.25±1.37 nm as confirmed by transmission electron microscopy (TEM). The UV-vis absorption spectrum shows a characteristic absorption peak of silver nanoparticles at 410 nm. FTIR confirms Azadirachtin as reducing and stabilizing agent for nanosilver formation. In addition, the nanosilver modified electrode (Ag/GC) exhibited an excellent electro-catalytic activity toward the reduction of hydrogen peroxide (H(2)O(2)). The produced nanosilver is stable and comparable in size. These silver nanoparticles show potential applications in the field of sensors, catalysis, fuel cells and nanodevices. Copyright © 2012 Elsevier B.V. All rights reserved.

Achieving high peak capacity production for gas chromatography and comprehensive two-dimensional gas chromatography by minimizing off-column peak broadening.

PubMed

Wilson, Ryan B; Siegler, W Christopher; Hoggard, Jamin C; Fitz, Brian D; Nadeau, Jeremy S; Synovec, Robert E

2011-05-27

By taking into consideration band broadening theory and using those results to select experimental conditions, and also by reducing the injection pulse width, peak capacity production (i.e., peak capacity per separation time) is substantially improved for one dimensional (1D-GC) and comprehensive two dimensional (GC×GC) gas chromatography. A theoretical framework for determining the optimal linear gas velocity (the linear gas velocity producing the minimum H), from experimental parameters provides an in-depth understanding of the potential for GC separations in the absence of extra-column band broadening. The extra-column band broadening is referred to herein as off-column band broadening since it is additional band broadening not due to the on-column separation processes. The theory provides the basis to experimentally evaluate and improve temperature programmed 1D-GC separations, but in order to do so with a commercial 1D-GC instrument platform, off-column band broadening from injection and detection needed to be significantly reduced. Specifically for injection, a resistively heated transfer line is coupled to a high-speed diaphragm valve to provide a suitable injection pulse width (referred to herein as modified injection). Additionally, flame ionization detection (FID) was modified to provide a data collection rate of 5kHz. The use of long, relatively narrow open tubular capillary columns and a 40°C/min programming rate were explored for 1D-GC, specifically a 40m, 180μm i.d. capillary column operated at or above the optimal average linear gas velocity. Injection using standard auto-injection with a 1:400 split resulted in an average peak width of ∼1.5s, hence a peak capacity production of 40peaks/min. In contrast, use of modified injection produced ∼500ms peak widths for 1D-GC, i.e., a peak capacity production of 120peaks/min (a 3-fold improvement over standard auto-injection). Implementation of modified injection resulted in retention time, peak width, peak height, and peak area average RSD%'s of 0.006, 0.8, 3.4, and 4.0%, respectively. Modified injection onto the first column of a GC×GC coupled with another high-speed valve injection onto the second column produced an instrument with high peak capacity production (500-800peaks/min), ∼5-fold to 8-fold higher than typically reported for GC×GC. Copyright © 2011 Elsevier B.V. All rights reserved.

Fabrication and surface-modification of implantable microprobes for neuroscience studies

NASA Astrophysics Data System (ADS)

Cao, H.; Nguyen, C. M.; Chiao, J. C.

2012-06-01

In this work implantable micro-probes for central nervous system (CNS) studies were developed on silicon and polyimide substrates. The probes which contained micro-electrode arrays with different surface modifications were designed for implantation in the CNS. The electrode surfaces were modified with nano-scale structures that could greatly increase the active surface area in order to enhance the electrochemical current outputs while maintaining micro-scale dimensions of the electrodes and probes. The electrodes were made of gold or platinum, and designed with different sizes. The silicon probes were modified by silicon nanowires fabricated with the vapor-liquid-solid mechanism at high temperatures. With polyimide substrates, the nanostructure modification was carried out by applying concentrated gold or silver colloid solutions onto the micro-electrodes at room temperature. The surfaces of electrodes before and after modification were observed by scanning electron microscopy. The silicon nanowire-modified surface was characterized by cyclic voltammetry. Experiments were carried out to investigate the improvement in sensing performance. The modified electrodes were tested with H2O2, electrochemical L-glutamate and dopamine. Comparisons between electrodes with and without nanostructure modification were conducted showing that the modifications have enhanced the signal outputs of the electrochemical neurotransmitter sensors.

Facile preparation of molecularly imprinted polypyrrole-graphene-multiwalled carbon nanotubes composite film modified electrode for rutin sensing.

PubMed

Yang, Lite; Yang, Juan; Xu, Bingjie; Zhao, Faqiong; Zeng, Baizhao

2016-12-01

In this paper, a novel molecularly imprinted composite film modified electrode was presented for rutin (RT) detection. The modified electrode was fabricated by electropolymerization of pyrrole on a graphene-multiwalled carbon nanotubes composite (G-MWCNTs) coated glassy carbon electrode in the presence of RT. The netlike G-MWCNTs composite, prepared by in situ hydrothermal process, had high conductivity and electrocatalytic activity. At the resulting MIP/G-MWCNTs/GCE electrode RT could produce a sensitive anodic peak in pH 1.87 Britton-Robinson buffer solution. The factors affecting the electrochemical behavior and response of RT on the modified electrode were carefully investigated and optimized. Under the selected conditions, the linear response range of RT was 0.01-1.0μmolL -1 and the detection limit (S/N=3) was 5.0nmolL -1 . The electrode was successfully applied to the determination of RT in buckwheat tea and orange juice samples, and the recoveries for standards added were 93.4-105%. Copyright © 2016 Elsevier B.V. All rights reserved.

ELECTROCHEMICAL DETERMINATION OF HYDROGEN SULFIDE AT CARBON NANOTUBE MODIFIED ELECTRODES. (R830900)

EPA Science Inventory

Carbon nanotube (CNT) modified glassy carbon electrodes exhibiting a strong and stable electrocatalytic response towards sulfide are described. A substantial (400 mV) decrease in the overvoltage of the sulfide oxidation reaction (compared to ordinary carbon electrodes) is...

Preparation of AN Electrode Modified with a Thermostable Enzyme BACILLUS Subtilis COTA by Electrodeposition

NASA Astrophysics Data System (ADS)

Watanabe, Toshio; Yamada, Yohei; Motonaka, Junko; Yabutani, Tomoki; Sakuraba, Haruhiko; Yasuzawa, Mikito

In this study, electrodeposition of thermostable enzyme Bacillus subtilis CotA, which is a laccase and has a bilirubin oxidase (BOD) activity, was investigated. The electrodeposition was operated in a mixture of Bacillus subtilis CotA in the PBS (pH 8.0) and TritonX-100 under applying potential (1100 mV vs. Ag/AgCl for 5 min.). The current response was measured by linear sweep voltammetry technique (LSV). The thermostable enzyme Bacillus subtilis CotA electrodeposited electrode was compared with a mesophile BOD electrodeposited electrode. As a result, the Bacillus subtilis CotA modified electrode showed better sensitivity and long-term stability than the mesophile BOD modified electrode.

Nucleoside-modified mRNA vaccines induce potent T follicular helper and germinal center B cell responses.

PubMed

Pardi, Norbert; Hogan, Michael J; Naradikian, Martin S; Parkhouse, Kaela; Cain, Derek W; Jones, Letitia; Moody, M Anthony; Verkerke, Hans P; Myles, Arpita; Willis, Elinor; LaBranche, Celia C; Montefiori, David C; Lobby, Jenna L; Saunders, Kevin O; Liao, Hua-Xin; Korber, Bette T; Sutherland, Laura L; Scearce, Richard M; Hraber, Peter T; Tombácz, István; Muramatsu, Hiromi; Ni, Houping; Balikov, Daniel A; Li, Charles; Mui, Barbara L; Tam, Ying K; Krammer, Florian; Karikó, Katalin; Polacino, Patricia; Eisenlohr, Laurence C; Madden, Thomas D; Hope, Michael J; Lewis, Mark G; Lee, Kelly K; Hu, Shiu-Lok; Hensley, Scott E; Cancro, Michael P; Haynes, Barton F; Weissman, Drew

2018-06-04

T follicular helper (Tfh) cells are required to develop germinal center (GC) responses and drive immunoglobulin class switch, affinity maturation, and long-term B cell memory. In this study, we characterize a recently developed vaccine platform, nucleoside-modified, purified mRNA encapsulated in lipid nanoparticles (mRNA-LNPs), that induces high levels of Tfh and GC B cells. Intradermal vaccination with nucleoside-modified mRNA-LNPs encoding various viral surface antigens elicited polyfunctional, antigen-specific, CD4 + T cell responses and potent neutralizing antibody responses in mice and nonhuman primates. Importantly, the strong antigen-specific Tfh cell response and high numbers of GC B cells and plasma cells were associated with long-lived and high-affinity neutralizing antibodies and durable protection. Comparative studies demonstrated that nucleoside-modified mRNA-LNP vaccines outperformed adjuvanted protein and inactivated virus vaccines and pathogen infection. The incorporation of noninflammatory, modified nucleosides in the mRNA is required for the production of large amounts of antigen and for robust immune responses. © 2018 Pardi et al.

Polymorphisms in mismatch repair genes are associated with risk and microsatellite instability of gastric cancer, and interact with life exposures.

PubMed

Zhu, Haifeng; Li, Xiaoqin; Zhang, Xiaomei; Chen, Deyu; Li, Dan; Ren, Jin; Gu, Hangang; Shu, Yongqian; Wang, Deqiang

2016-03-15

Epigenetic alterations of DNA mismatch repair (MMR) genes are associated with risk of gastric cancer (GC) by causing microsatellite instability (MSI). Less understood is the association of common polymorphisms in MMR genes with the risk and MSI phenotype of GC. A hospital-based study was conducted in China with 423 cases and 454 matched controls. Four potentially functional polymorphisms were selected and analyzed: rs1800734 in MLH1, rs2303428 in MSH2, rs735943 in EXO1, and rs11797 in TREX1. The rs1800734 G-allele was associated with decreased risk of GC (GA or GG vs AA, OR=0.72; 95% CI: 0.50-1.05; Ptrend=0.029). For combined effects, a dose-response manner was observed in which GC risk was increased with increasing number of at-risk genotypes (Ptrend=0.039); this manner mainly existed in MSI GC (Ptrend=0.047) rather than in microsatellite stability GC, though neither single polymorphism was linked with MSI. For exposures, modified effects were observed from green tea drinking and soy foods intake on rs11797 (P for interaction=0.007 and 0.016, respectively). The MLH1 rs1800734 polymorphism is associated with GC risk. Those at-risk genotypes have a joint effect on GC risk, which contributes to the MSI phenotype of GC. Life exposures modify GC risk, stratified by MMR genotypes. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation of Gc protein-derived macrophage activating factor (GcMAF) and its structural characterization and biological activities.

PubMed

Mohamad, Saharuddin Bin; Nagasawa, Hideko; Uto, Yoshihiro; Hori, Hitoshi

2002-01-01

Gc protein has been reported to be a precursor of Gc protein-derived macrophage activation factor (GcMAF) in the inflammation-primed macrophage activation cascade. An inducible beta-galactosidase of B cells and neuraminidase of T cells convert Gc protein to GcMAF. Gc protein from human serum was purified using 25(OH)D3 affinity column chromatography and modified to GcMAF using immobilized glycosidases (beta-galactosidase and neuraminidase) The sugar moiety structure of GcMAF was characterized by lectin blotting by Helix pomatia agglutinin. The biological activities of GcMAF were evaluated by a superoxide generation assay and a phagocytosis assay. We successfully purified Gc protein from human serum. GcMAF was detected by lectin blotting and showed a high biological activity. Our results support the importance of the terminal N-acetylgalactosamine moiety in the GcMAF-mediated macrophage activation cascade, and the existence of constitutive GcMAF in human serum. These preliminary data are important for designing small molecular GcMAF mimics.

Gold nanoparticles embedded electropolymerized thin film of pyrimidine derivative on glassy carbon electrode for highly sensitive detection of l-cysteine.

PubMed

Kannan, Ayyadurai; Sevvel, Ranganathan

2017-09-01

This paper demonstrates the fabrication of novel gold nanoparticles incorporated poly (4-amino-6-hydroxy-2-mercaptopyrimidine) (Nano-Au/Poly-AHMP) film modified glassy carbon electrode and it is employed for highly sensitive detection of l-cysteine (CYS). The modified electrode was characterized by scanning electron microscope (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). SEM images of modified electrode revealed the homogeneous distribution of gold nanoparticles on poly (4-amino-6-hydroxy-2-mercaptopyrimidine) thin film modified glassy carbon electrode. The modified electrode was successfully utilized for highly selective and sensitive determination of l-cysteine at physiological pH7.0. The present electrochemical sensor successfully resolved the voltammetric signals of ascorbic acid (AA) and l-cysteine with peak separation of 0.510V. To the best of our knowledge, this is the first report of larger peak separation between AA and CYS. Wide linear concentration ranges (2μM-500μM), low detection limit (0.020μM), an excellent reproducibility and stability are achieved for cysteine sensing with this Nano-Au/Poly-AHMP/GCE. Copyright © 2017 Elsevier B.V. All rights reserved.

Strategies for an enzyme immobilization on electrodes: Structural and electrochemical characterizations

NASA Astrophysics Data System (ADS)

Ganesh, V.; Muthurasu, A.

2012-04-01

In this paper, we propose various strategies for an enzyme immobilization on electrodes (both metal and semiconductor electrodes). In general, the proposed methodology involves two critical steps viz., (1) chemical modification of substrates using functional monolayers [Langmuir - Blodgett (LB) films and/or self-assembled monolayers (SAMs)] and (2) anchoring of a target enzyme using specific chemical and physical interactions by attacking the terminal functionality of the modified films. Basically there are three ways to immobilize an enzyme on chemically modified electrodes. First method consists of an electrostatic interaction between the enzyme and terminal functional groups present within the chemically modified films. Second and third methods involve the introduction of nanomaterials followed by an enzyme immobilization using both the physical and chemical adsorption processes. As a proof of principle, in this work we demonstrate the sensing and catalytic activity of horseradish peroxidase (HRP) anchored onto SAM modified indium tin oxide (ITO) electrodes towards hydrogen peroxide (H2O2). Structural characterization of such modified electrodes is performed using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measurements. The binding events and the enzymatic reactions are monitored using electrochemical techniques mainly cyclic voltammetry (CV).

Direct electron transfer of Phanerochaete chrysosporium cellobiose dehydrogenase at platinum and palladium nanoparticles decorated carbon nanotubes modified electrodes.

PubMed

Bozorgzadeh, Somayyeh; Hamidi, Hassan; Ortiz, Roberto; Ludwig, Roland; Gorton, Lo

2015-10-07

In the present work, platinum and palladium nanoparticles (PtNPs and PdNPs) were decorated on the surface of multi-walled carbon nanotubes (MWCNTs) by a simple thermal decomposition method. The prepared nanohybrids, PtNPs-MWCNTs and PdNPs-MWCNTs, were cast on the surface of spectrographic graphite electrodes and then Phanerochaete chrysosporium cellobiose dehydrogenase (PcCDH) was adsorbed on the modified layer. Direct electron transfer between PcCDH and the nanostructured modified electrodes was studied using flow injection amperometry and cyclic voltammetry. The maximum current responses (Imax) and the apparent Michaelis-Menten constants (K) for the different PcCDH modified electrodes were calculated by fitting the data to the Michaelis-Menten equation and compared. The sensitivity towards lactose was 3.07 and 3.28 μA mM(-1) at the PcCDH/PtNPs-MWCNTs/SPGE and PcCDH/PdNPs-MWCNTs/SPGE electrodes, respectively, which were higher than those measured at the PcCDH/MWCNTs/SPGE (2.60 μA mM(-1)) and PcCDH/SPGE (0.92 μA mM(-1)). The modified electrodes were additionally tested as bioanodes for biofuel cell applications.

Modified Electrodes Used for Electrochemical Detection of Metal Ions in Environmental Analysis

PubMed Central

March, Gregory; Nguyen, Tuan Dung; Piro, Benoit

2015-01-01

Heavy metal pollution is one of the most serious environmental problems, and regulations are becoming stricter. Many efforts have been made to develop sensors for monitoring heavy metals in the environment. This review aims at presenting the different label-free strategies used to develop electrochemical sensors for the detection of heavy metals such as lead, cadmium, mercury, arsenic etc. The first part of this review will be dedicated to stripping voltammetry techniques, on unmodified electrodes (mercury, bismuth or noble metals in the bulk form), or electrodes modified at their surface by nanoparticles, nanostructures (CNT, graphene) or other innovative materials such as boron-doped diamond. The second part will be dedicated to chemically modified electrodes especially those with conducting polymers. The last part of this review will focus on bio-modified electrodes. Special attention will be paid to strategies using biomolecules (DNA, peptide or proteins), enzymes or whole cells. PMID:25938789

Electrochemical detection of phenolic estrogenic compounds at clay modified carbon paste electrode

NASA Astrophysics Data System (ADS)

Belkamssa, N.; Ouattara, L.; Kawachi, A.; Tsujimura, M.; Isoda, H.; Chtaini, A.; Ksibi, M.

2015-04-01

A simple and sensitive electroanalytical method was developed to determine the Endocrine Disrupting chemical 4-tert-octylphenol on clay modified carbon paste electrode (Clay/CPE). The electrochemical response of the proposed electrode was studied by means of cyclic and square wave voltammetry. It has found that the oxidation of 4-tert-octylphenol on the clay/CPE displayed a well-defined oxidation peak. Under these optimal conditions, a linear relation between concentrations of 4-tert-octylphenol current response was obtained over range of 7.26×10-6 to 3.87×10-7 with a detection and quantification limit of 9.2×10-7 M and 3.06×10-6 M, respectively. The correlation coefficient is 0.9963. The modified electrode showed suitable sensitivity, high stability and an accurate detection of 4-tert-octylphenol. The modified electrode also relevant suitable selectivity for various phenolic estrogenic compounds.

Layer-by-Layer Assembly of Glucose Oxidase on Carbon Nanotube Modified Electrodes.

PubMed

Suroviec, Alice H

2017-01-01

The use of enzymatically modified electrodes for the detection of glucose or other non-electrochemically active analytes is becoming increasingly common. Direct heterogeneous electron transfer to glucose oxidase has been shown to be kinetically difficult, which is why electron transfer mediators or indirect detection is usually used for monitoring glucose with electrochemical sensors. It has been found, however, that electrodes modified with single or multi-walled carbon nanotubes (CNTs) demonstrate fast heterogeneous electron transfer kinetics as compared to that found for traditional electrodes. Incorporating CNTs into the assembly of electrochemical glucose sensors, therefore, affords the possibility of facile electron transfer to glucose oxidase, and a more direct determination of glucose. This chapter describes the methods used to use CNTs in a layer-by-layer structure along with glucose oxidase to produce an enzymatically modified electrode with high turnover rates, increased stability and shelf-life.

Carbon materials modified by plasma treatment as electrodes for supercapacitors

NASA Astrophysics Data System (ADS)

Lota, Grzegorz; Tyczkowski, Jacek; Kapica, Ryszard; Lota, Katarzyna; Frackowiak, Elzbieta

The carbon material was modified by RF plasma with various reactive gases: O 2, Ar and CO 2. Physicochemical properties of the final carbon products were characterized using different techniques such as gas adsorption method and XPS. Plasma modified materials enriched in oxygen functionalities were investigated as electrodes for supercapacitors in acidic medium. The electrochemical measurements have been carried out using cyclic voltammetry, galvanostatic charge/discharge and impedance spectroscopy. The electrochemical measurements have confirmed that capacity characteristics are closely connected with a type of plasma exposition. Modification processes have an influence on the kind and amount of surface functional groups in the carbon matrix. The moderate increase of capacity of carbon materials modified by plasma has been observed using symmetric two-electrode systems. Whereas investigations made in three-electrode system proved that the suitable selection of plasma modification parameters allows to obtain promising negative and positive electrode materials for supercapacitor application.

An electrochemical fungicide pyrimethanil sensor based on carbon nanotubes/ionic-liquid construction modified electrode.

PubMed

Yang, Jichun; Wang, Qiong; Zhang, Minhui; Zhang, Shuming; Zhang, Lei

2015-11-15

In this study, a simple, rapid, sensitive and environmentally friendly electroanalytical detection method for pyrimethanil (PMT) was developed, which was based on multi-walled carbon nanotubes (MWCNTs) and ionic liquids (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) modified glassy carbon electrode (GCE). MWCNTs-IL modified electrode significantly enhanced the oxidation peak current of PMT by combining the excellent electrochemical properties of MWCNTs and IL, suggesting that the modified electrode can remarkably improve the sensitivity of PMT detection. Under the optimum conditions, this electrochemical sensor exhibited a linear concentration range for PMT of 1.0 × 10(-7)-1.0 × 10(-4) mol L(-1) and the detection limit was 1.6 × 10(-8) mol L(-1) (S/N = 3). The fabricated electrode showed good reproducibility, stability and anti-interference, and also it was successfully employed to detect PMT in real samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

Modified Method for Detection of Benzoylecgonine in Human Urine by GC-MS: Derivatization Using Pentafluoropropanol/Acetic Anhydride.

PubMed

Serafin, Michelle C; Paulemon, Kasandra M; Fuller, Zachary J; Bronner, William E

2017-05-01

An existing GC-MS method for detecting benzoylecgonine (BZE) in urine was modified by changing derivatizing reagents. This method modification presents a cost-effective alternative derivatization procedure for the detection of BZE in urine by GC-MS. The combination of pentafluoropropanol and acetic anhydride was found to produce the same reaction product for BZE as pentafluoropropanol with pentafluoropropionic anhydride, while reducing reagent cost. With no anhydride present, derivatization of BZE by pentafluoropropanol did not occur. Published by Oxford University Press 2017. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Performance of polyacrylonitrile-carbon nanotubes composite on carbon cloth as electrode material for microbial fuel cells.

PubMed

Kim, Sun-Il; Lee, Jae-Wook; Roh, Sung-Hee

2011-02-01

The performance of carbon nanotubes composite-modified carbon cloth electrodes in two-chambered microbial fuel cell (MFC) was investigated. The electrode modified with polyacrylonitrile-carbon nanotubes (PAN-CNTs) composite showed better electrochemical performance than that of plain carbon cloth. The MFC with the composite-modified anode containing 5 mg/cm2 PAN-CNTs exhibited a maximum power density of 480 mW/m2.

Sensitive detection of hydroxylamine at a simple baicalin carbon nanotubes modified electrode.

PubMed

Zhang, Hongfang; Zheng, Jianbin

2012-05-15

A baicalin multi-wall carbon nanotubes (BaMWCNT) modified glassy carbon electrode (GCE) for the sensitive determination of hydroxylamine was described. The BaMWCNT/GCE with dramatic stability was firstly fabricated with a simple adsorption method. And it showed excellent catalytic activity toward the electrooxidation of hydroxylamine. The amperometric response at the BaMWCNT/GCE modified electrode increased linearly to hydroxylamine concentrations in the range of 0.5 μM to 0.4mM with a detection limit of 0.1 μM. The modified electrode was applied to detection hydroxylamine in the tap water, and the average recovery for the standards added was 96.0%. Copyright © 2012 Elsevier B.V. All rights reserved.

Determination of heavy metals in mussel and oyster samples with tris (2,2‧-bipyridyl) ruthenium (II)/graphene/Nafion® modified glassy carbon electrodes

NASA Astrophysics Data System (ADS)

Palisoc, Shirley T.; Uy, Donald Jans S.; Natividad, Michelle T.; Lopez, Toni Beth G.

2017-11-01

Tris (2,2‧-bipyridyl)ruthenium(II)/graphene/Nafion® modified glassy carbon electrodes (GCEs) were fabricated using the drop coating method. The modified electrode was used as the working electrode in differential pulse voltammetry (DPV) for the determination of lead, cadmium, and copper in mussel and oyster samples. The concentration of Tris (2,2‧-bipyridyl) ruthenium (II) and graphene were varied while those of Nafion®, methanol, and ethanol were held constant in the coating solution. The morphology and elemental composition of the fabricated electrodes were analyzed by scanning electron microscopy and energy-dispersive x-ray spectroscopy. Cyclic voltammetry (CV) was done to investigate the reversibility and stability of the modified electrodes. The modified electrode with the best figures of merit was utilized for the detection of copper (Cu2+), lead (Pb2+) and cadmium (Cd2+) via DPV. This was the electrode modified with 4 mg [Ru (bpy)3]2+ and 3 mg graphene. The anodic current and metal concentration showed linear relationship in the range of 48 ppb-745 ppb for Pb2+, 49 ppb-613 ppb for Cd2+, and 28 ppb-472 ppb for Cu2+. The limits of detection for lead, cadmium, and copper were 48 ppb, 49 ppb, and 28 ppb, respectively. Results from atomic absorption spectrometry (AAS) were compared with those measured with DPV. Lead, cadmium, and copper were in mussels, oysters, and sea water. In addition, DPV was able to detect other metals such as zinc, iron, tin and mercury in sea water samples and some samples of oysters.

Interfacial characterization and supercapacitive properties of polyaniline-Gum arabic nanocomposite/graphene oxide LbL modified electrodes

NASA Astrophysics Data System (ADS)

Oliveira, Rafaela D.; Santos, Cleverson S.; Ferreira, Rodolfo T.; Marciniuk, Gustavo; Marchesi, Luís F.; Garcia, Jarem R.; Vidotti, Marcio; Pessoa, Christiana A.

2017-12-01

In this manuscript, we describe the synthesis and electrochemical characterization of polyaniline-gum arabic nanocomposites and graphene oxide (PANI-GA/GO) modified electrodes with a detailed study concerning their supercapacitive properties. The electrode modification was carried out by using the Layer-by-Layer technique (LbL), where the PANI-GA nanocomposite dispersion was used as polycation and the GO colloidal dispersion as polyanion. The bilayer growth was followed by both UV-vis spectroscopy and cyclic voltammetry, and an increase in the characteristic PANI absorption and in the electrochemical signal was verified, confirming the electrode build up. Galvanostatic charge-discharge curves (GCDC) were performed to evaluate the supercapacitive properties of the modified electrodes, these results showed the dependence of the specific capacitance with the number of bilayers, where values of CS around 15 mF cm-2 (i = 0.1 mA cm-2) were found. Electrochemical impedance spectroscopy confirmed the pseudocapacitive properties of the modified electrodes, showing an increase in the low-frequency capacitance with the number of bilayers. Hereby the (PANI-GA/GO)-LbL electrodes were shown to be good candidates for active materials in supercapacitors.

Derivatization of single-walled carbon nanotubes with redox mediator for biocatalytic oxygen electrodes.

PubMed

Sadowska, K; Stolarczyk, K; Biernat, J F; Roberts, K P; Rogalski, J; Bilewicz, R

2010-11-01

Single-walled carbon nanotubes (SWCNTs) were covalently modified with a redox mediator derived from 2,2'-azino-bis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS), and implemented in the construction of electrodes for biocatalytic oxygen reduction. The procedure is based on: covalent bonding of mediator to nanotubes, placing the nanotubes directly on the carbon electrode surface and covering the nanostructured electrode with a Nafion film containing laccase as the biocatalyst. The modified electrode is stable and the problem of mediator (ABTS) leaking from the film is eliminated by binding it covalently to the nanotubes. Three different synthetic approaches were used to obtain ABTS-modified carbon nanotubes. Nanotubes were modified at ends/defect sites or on the nanotube sidewalls and characterized by Raman spectroscopy, TGA and electrochemistry. The accessibility of differently located ABTS units by the laccase active center and mediation of electron transfer were studied by cyclic voltammetry. The surface concentrations of ABTS groups electrically connected with the electrode were compared for each of the electrodes based on the charges of the voltammetric peaks recorded in the deaerated solution. The nanotube modification procedure giving the best parameters of the catalytic process was selected. Copyright © 2010 Elsevier B.V. All rights reserved.

Electrochemistry of Canis familiaris cytochrome P450 2D15 with gold nanoparticles: An alternative to animal testing in drug discovery.

PubMed

Rua, Francesco; Sadeghi, Sheila J; Castrignanò, Silvia; Valetti, Francesca; Gilardi, Gianfranco

2015-10-01

This work reports for the first time the direct electron transfer of the Canis familiaris cytochrome P450 2D15 on glassy carbon electrodes to provide an analytical tool as an alternative to P450 animal testing in the drug discovery process. Cytochrome P450 2D15, that corresponds to the human homologue P450 2D6, was recombinantly expressed in Escherichia coli and entrapped on glassy carbon electrodes (GC) either with the cationic polymer polydiallyldimethylammonium chloride (PDDA) or in the presence of gold nanoparticles (AuNPs). Reversible electrochemical signals of P450 2D15 were observed with calculated midpoint potentials (E1/2) of −191 ± 5 and −233 ± 4 mV vs. Ag/AgCl for GC/PDDA/2D15 and GC/AuNPs/2D15, respectively. These experiments were then followed by the electro-catalytic activity of the immobilized enzyme in the presence of metoprolol. The latter drug is a beta-blocker used for the treatment of hypertension and is a specific marker of the human P450 2D6 activity. Electrocatalysis data showed that only in the presence of AuNps the expected α-hydroxy-metoprolol product was present as shown by HPLC. The successful immobilization of the electroactive C. familiaris cytochrome P450 2D15 on electrode surfaces addresses the ever increasing demand of developing alternative in vitromethods for amore detailed study of animal P450 enzymes' metabolism, reducing the number of animals sacrificed in preclinical tests.

Beyond graphene: Electrochemical sensors and biosensors for biomarkers detection.

PubMed

Bollella, Paolo; Fusco, Giovanni; Tortolini, Cristina; Sanzò, Gabriella; Favero, Gabriele; Gorton, Lo; Antiochia, Riccarda

2017-03-15

Graphene's success has stimulated great interest and research in the synthesis and characterization of graphene-like 2D materials, single and few-atom-thick layers of van der Waals materials, which show fascinating and technologically useful properties. This review presents an overview of recent electrochemical sensors and biosensors based on graphene and on graphene-like 2D materials for biomarkers detection. Initially, we will outline different electrochemical sensors and biosensors based on chemically derived graphene, including graphene oxide and reduced graphene oxide, properly functionalized for improved performances and we will discuss the various strategies to prepare graphene modified electrodes. Successively, we present electrochemical sensors and biosensors based on graphene-like 2D materials, such as boron nitride (BN), graphite-carbon nitride (g-C 3 N 4 ), transition metal dichalcogenides (TMDs), transition metal oxides and graphane, outlining how the new modified 2D nanomaterials will improve the electrochemical performances. Finally, we will compare the results obtained with different sensors and biosensors for the detection of important biomarkers such as glucose, hydrogen peroxide and cancer biomarkers and highlight the advantages and disadvantages of the use of graphene and graphene-like 2D materials in different sensing platforms. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of kojic acid based on the interface enhancement effects of carbon nanotube/alizarin red S modified electrode.

PubMed

Liu, Jieshu; Zhou, Dazhai; Liu, Xiaopeng; Wu, Kangbing; Wan, Chidan

2009-04-01

Based on non-covalent interactions such as pi-pi stacking, van der Waals interactions and strong adsorption, alizarin red S (ARS) interacts with multi-walled carbon nanotubes (MWNT), improving the solubility of MWNT in water and resulting in a stable MWNT/ARS solution. By successive cyclic sweeps between 0.0 and 2.2V in the MWNT/ARS solution, a MWNT/ARS composite film was fabricated on an electrode surface. The electrochemical behaviors of kojic acid at the bare electrode, the ARS film-modified electrode and the MWNT/ARS film-modified electrode were investigated. It was found that the oxidation signal of kojic acid significantly increased at the MWNT/ARS film-modified electrode, which was attributed to the unique properties of MWNT such as large surface area, strong adsorptive ability and subtle electronic character. The effects of pH and cyclic number of electropolymerization were examined. A rapid, sensitive and simple electrochemical method was then developed for the determination of kojic acid. This method exhibits good linearity over the range from 4.0 x 10(-7) to 6.0 x 10(-5)mol L(-1), and the limit of detection is as low as 1.0 x 10(-7)mol L(-1). In order to validate feasibility, the MWNT/ARS film-modified electrode was used for quantitative analysis of kojic acid in food samples.

Improving the power generation of microbial fuel cells by modifying the anode with single-wall carbon nanohorns.

PubMed

Yang, Jiawei; Cheng, Shaoan; Sun, Yi; Li, Chaochao

2017-10-01

To increase the power generation of microbial fuel cells (MFCs), anode modification with carbon materials (activated carbon, carbon nanotubes, and carbon nanohorns) was investigated. Maximum power densities of a stainless-steel anode MFC with a non-modified electrode (SS-MFC), an activated carbon-modified electrode (AC-MFC), a carbon nanotube-modified electrode (CNT-MFC) and a carbon nanohorn-modified electrode (CNH-MFC) were 72, 244, 261 and 327 mW m -2 , respectively. The total polarization resistance measured by electrochemical impedance spectroscopy were 3610 Ω for SS-MFC, 283 Ω for AC-MFC, 231 Ω for CNTs-MFC, and 136 Ω for CNHs-MFC, consistent with the anode resistances obtained by fitting the anode polarization curves. Single-wall carbon nanohorns are better than activated carbon and carbon nanotubes as a new anode modification material for improving anode performance.

Synthesis and electrocatalytic activity of Au/Pt bimetallic nanodendrites for ethanol oxidation in alkaline medium.

PubMed

Han, Xinyi; Wang, Dawei; Liu, Dong; Huang, Jianshe; You, Tianyan

2012-02-01

Gold/Platinum (Au/Pt) bimetallic nanodendrites were successfully synthesized through seeded growth method using preformed Au nanodendrites as seeds and ascorbic acid as reductant. Cyclic voltammograms (CVs) of a series of Au/Pt nanodendrites modified electrodes in 1M KOH solution containing 1M ethanol showed that the electrocatalyst with a molar ratio (Au:Pt) of 3 exhibited the highest peak current density and the lowest onset potential. The peak current density of ethanol electro-oxidation on the Au(3)Pt(1) nanodendrites modified glassy carbon electrode (Au(3)Pt(1) electrode) is about 16, 12.5, and 4.5 times higher than those on the polycrystalline Pt electrode, polycrystalline Au electrode, and Au nanodendrites modified glassy carbon electrode (Au dendrites electrode), respectively. The oxidation peak potential of ethanol electro-oxidation on the Au(3)Pt(1) electrode is about 299 and 276 mV lower than those on the polycrystalline Au electrode and Au dendrites electrode, respectively. These results demonstrated that the Au/Pt bimetallic nanodendrites may find potential application in alkaline direct ethanol fuel cells (ADEFCs). Copyright © 2011 Elsevier Inc. All rights reserved.

Surface modification of GC and HOPG with diazonium, amine, azide, and olefin derivatives.

PubMed

Tanaka, Mutsuo; Sawaguchi, Takahiro; Sato, Yukari; Yoshioka, Kyoko; Niwa, Osamu

2011-01-04

Surface modification of glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG) was carried out with diazonium, amine, azide, and olefin derivatives bearing ferrocene as an electroactive moiety. Features of the modified surfaces were evaluated by surface concentrations of immobilized molecule, blocking effect of the modified surface against redox reaction, and surface observation using cyclic voltammetry and electrochemical scanning tunneling microscope (EC-STM). The measurement of surface concentrations of immobilized molecule revealed the following three aspects: (i) Diazonium and olefin derivatives could modify substrates with the dense-monolayer concentration. (ii) The surface concentration of immobilized amine derivative did not reach to the dense-monolayer concentration reflecting their low reactivity. (iii) The surface modification with the dense-monolayer concentration was also possible with azide derivative, but the modified surface contained some oligomers produced by the photoreaction of azides. Besides, the blocking effect against redox reaction was observed for GC modified with diazonium derivative and for HOPG modified with diazonium and azide derivatives, suggesting fabrication of a densely modified surface. Finally, the surface observation for HOPG modified with diazonium derivative by EC-STM showed a typical monolayer structure, in which the ferrocene moieties were packed densely at random. On the basis of those results, it was demonstrated that surface modification of carbon substrates with diazonium could afford a dense monolayer similar to the self-assembled monolayer (SAM) formation.

Sensitive and selective determination of Cu2+ at D-penicillamine functionalized nano-cellulose modified pencil graphite electrode

NASA Astrophysics Data System (ADS)

Taheri, M.; Ahour, F.; Keshipour, S.

2018-06-01

A novel electrochemical sensor based on D-penicillamine anchored nano-cellulose (DPA-NC) modified pencil graphite electrode was fabricated and used for highly selective and sensitive determination of copper (II) ions in the picomolar concentration by square wave adsorptive stripping voltammetric (SWV) method. The modified electrode showed better and increased SWV response compared to the bare and NC modified electrodes which may be related to the porous structure of modifier along with formation of complex between Cu2+ ions and nitrogen or oxygen containing groups in DPA-NC. Optimization of various experimental parameters influence the performance of the sensor, were investigated. Under optimized condition, DPA-NC modified electrode was used for the analysis of Cu2+ in the concentration range from 0.2 to 50 pM, and a lower detection limit of 0.048 pM with good stability, repeatability, and selectivity. Finally, the practical applicability of DPA-NC-PGE was confirmed via measuring trace amount of Cu (II) in tap and river water samples.

Ag Nanoparticles-Modified 3D Graphene Foam for Binder-Free Electrodes of Electrochemical Sensors.

PubMed

Han, Tao; Jin, Jianli; Wang, Congxu; Sun, Youyi; Zhang, Yinghe; Liu, Yaqing

2017-02-16

Ag nanoparticles-modified 3D graphene foam was synthesized through a one-step in-situ approach and then directly applied as the electrode of an electrochemical sensor. The composite foam electrode exhibited electrocatalytic activity towards Hg(II) oxidation with high limit of detection and sensitivity of 0.11 μM and 8.0 μA/μM, respectively. Moreover, the composite foam electrode for the sensor exhibited high cycling stability, long-term durability and reproducibility. These results were attributed to the unique porous structure of the composite foam electrode, which enabled the surface of Ag nanoparticles modified reduced graphene oxide (Ag NPs modified rGO) foam to become highly accessible to the metal ion and provided more void volume for the reaction with metal ion. This work not only proved that the composite foam has great potential application in heavy metal ions sensors, but also provided a facile method of gram scale synthesis 3D electrode materials based on rGO foam and other electrical active materials for various applications.

Ag Nanoparticles-Modified 3D Graphene Foam for Binder-Free Electrodes of Electrochemical Sensors

PubMed Central

Han, Tao; Jin, Jianli; Wang, Congxu; Sun, Youyi; Zhang, Yinghe; Liu, Yaqing

2017-01-01

Ag nanoparticles-modified 3D graphene foam was synthesized through a one-step in-situ approach and then directly applied as the electrode of an electrochemical sensor. The composite foam electrode exhibited electrocatalytic activity towards Hg(II) oxidation with high limit of detection and sensitivity of 0.11 µM and 8.0 µA/µM, respectively. Moreover, the composite foam electrode for the sensor exhibited high cycling stability, long-term durability and reproducibility. These results were attributed to the unique porous structure of the composite foam electrode, which enabled the surface of Ag nanoparticles modified reduced graphene oxide (Ag NPs modified rGO) foam to become highly accessible to the metal ion and provided more void volume for the reaction with metal ion. This work not only proved that the composite foam has great potential application in heavy metal ions sensors, but also provided a facile method of gram scale synthesis 3D electrode materials based on rGO foam and other electrical active materials for various applications. PMID:28336878

Electrochemical Oxidation of EDTA in Nuclear Wastewater Using Platinum Supported on Activated Carbon Fibers

PubMed Central

Zhao, Bo; Zhu, Wenkun; Mu, Tao; Hu, Zuowen; Duan, Tao

2017-01-01

A novel Pt/ACF (Pt supported on activated carbon fibers) electrode was successfully prepared with impregnation and electrodeposition method. Characterization of the electrodes indicated that the Pt/ACF electrode had a larger effective area and more active sites. Electrochemical degradation of ethylenediaminetetra-acetic acid (EDTA) in aqueous solution with Pt/ACF electrodes was investigated. The results showed that the 3% Pt/ACF electrode had a better effect on EDTA removal. The operational parameters influencing the electrochemical degradation of EDTA with 3% Pt/ACF electrode were optimized and the optimal removal of EDTA and chemical oxygen demand (COD) were 94% and 60% after 100 min on condition of the electrolyte concentration, initial concentration of EDTA, current density and initial value of pH were 0.1 mol/L, 300 mg/L, 40 mA/cm2 and 5.0, respectively. The degradation intermediates of EDTA in electrochemical oxidation with 3% Pt/ACF electrode were identified by gas chromatography-mass spectrum (GC-MS). PMID:28754016

Electrochemical properties of seamless three-dimensional carbon nanotubes-grown graphene modified with horseradish peroxidase.

PubMed

Komori, Kikuo; Terse-Thakoor, Trupti; Mulchandani, Ashok

2016-10-01

Horseradish peroxidase (HRP) was immobilized through sodium dodecyl sulfate (SDS) on the surface of a seamless three-dimensional hybrid of carbon nanotubes grown at the graphene surface (HRP-SDS/CNTs/G) and its electrochemical properties were investigated. Compared with graphene alone electrode modified with HRP via SDS (HRP-SDS/G electrode), the surface coverage of electroactive HRP at the CNTs/G electrode surface was approximately 2-fold greater because of CNTs grown at the graphene surface. Based on the increase in the surface coverage of electroactive HRP, the sensitivity to H2O2 at the HRP-SDS/CNTs/G electrode was higher than that at the HRP-SDS/G electrode. The kinetics of the direct electron transfer from the CNTs/G electrode to compound I and II of modified HRP was also analyzed. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of electrode materials on the space charge distribution of an Al2O3 nano-modified transformer oil under impulse voltage conditions

NASA Astrophysics Data System (ADS)

Yang, Qing; Liu, Mengna; Sima, Wenxia; Jin, Yang

2017-11-01

The combined effect mechanism of electrode materials and Al2O3 nanoparticles on the insulating characteristics of transformer oil was investigated. Impulse breakdown tests of pure transformer oil and Al2O3 nano-modified transformer oil of varying concentrations with different electrode materials (brass, aluminum and stainless steel) showed that the breakdown voltage of Al2O3 nano-modified transformer oil is higher than that of pure transformer oil and there is a there is an optimum concentration for Al2O3 nanoparticles when the breakdown voltage reaches the maximum. In addition, the breakdown voltage was highest with the brass electrode, followed by that with stainless steel and then aluminum, irrespective of the concentration of nanoparticles in the transformer oil. This is explained by the charge injection patterns from different electrode materials according to the results of space charge measurements in pure and nano-modified transformer oil using the Kerr electro-optic system. The test results indicate that there are electrode-dependent differences in the charge injection patterns and quantities and then the electric field distortion, which leads to the difference breakdown strength in result. As for the nano-modified transformer oil, due to the Al2O3 nanoparticle’s ability of shielding space charges of different polarities and the charge injection patterns of different electrodes, these two factors have different effects on the electric field distribution and breakdown process of transformer oil between different electrode materials. This paper provides a feasible approach to exploring the mechanism of the effect of the electrode material and nanoparticles on the breakdown strength of liquid dielectrics and analyzing the breakdown process using the space charge distribution.

Cellobiose Dehydrogenase Aryl Diazonium Modified Single Walled Carbon Nanotubes: Enhanced Direct Electron Transfer through a Positively Charged Surface

PubMed Central

2011-01-01

One of the challenges in the field of biosensors and biofuel cells is to establish a highly efficient electron transfer rate between the active site of redox enzymes and electrodes to fully access the catalytic potential of the biocatalyst and achieve high current densities. We report on very efficient direct electron transfer (DET) between cellobiose dehydrogenase (CDH) from Phanerochaete sordida (PsCDH) and surface modified single walled carbon nanotubes (SWCNT). Sonicated SWCNTs were adsorbed on the top of glassy carbon electrodes and modified with aryl diazonium salts generated in situ from p-aminobenzoic acid and p-phenylenediamine, thus featuring at acidic pH (3.5 and 4.5) negative or positive surface charges. After adsorption of PsCDH, both electrode types showed excellent long-term stability and very efficient DET. The modified electrode presenting p-aminophenyl groups produced a DET current density of 500 μA cm−2 at 200 mV vs normal hydrogen reference electrode (NHE) in a 5 mM lactose solution buffered at pH 3.5. This is the highest reported DET value so far using a CDH modified electrode and comes close to electrodes using mediated electron transfer. Moreover, the onset of the electrocatalytic current for lactose oxidation started at 70 mV vs NHE, a potential which is 50 mV lower compared to when unmodified SWCNTs were used. This effect potentially reduces the interference by oxidizable matrix components in biosensors and increases the open circuit potential in biofuel cells. The stability of the electrode was greatly increased compared with unmodified but cross-linked SWCNTs electrodes and lost only 15% of the initial current after 50 h of constant potential scanning. PMID:21417322

Cellobiose dehydrogenase aryl diazonium modified single walled carbon nanotubes: enhanced direct electron transfer through a positively charged surface.

PubMed

Tasca, Federico; Harreither, Wolfgang; Ludwig, Roland; Gooding, John Justin; Gorton, Lo

2011-04-15

One of the challenges in the field of biosensors and biofuel cells is to establish a highly efficient electron transfer rate between the active site of redox enzymes and electrodes to fully access the catalytic potential of the biocatalyst and achieve high current densities. We report on very efficient direct electron transfer (DET) between cellobiose dehydrogenase (CDH) from Phanerochaete sordida (PsCDH) and surface modified single walled carbon nanotubes (SWCNT). Sonicated SWCNTs were adsorbed on the top of glassy carbon electrodes and modified with aryl diazonium salts generated in situ from p-aminobenzoic acid and p-phenylenediamine, thus featuring at acidic pH (3.5 and 4.5) negative or positive surface charges. After adsorption of PsCDH, both electrode types showed excellent long-term stability and very efficient DET. The modified electrode presenting p-aminophenyl groups produced a DET current density of 500 μA cm(-2) at 200 mV vs normal hydrogen reference electrode (NHE) in a 5 mM lactose solution buffered at pH 3.5. This is the highest reported DET value so far using a CDH modified electrode and comes close to electrodes using mediated electron transfer. Moreover, the onset of the electrocatalytic current for lactose oxidation started at 70 mV vs NHE, a potential which is 50 mV lower compared to when unmodified SWCNTs were used. This effect potentially reduces the interference by oxidizable matrix components in biosensors and increases the open circuit potential in biofuel cells. The stability of the electrode was greatly increased compared with unmodified but cross-linked SWCNTs electrodes and lost only 15% of the initial current after 50 h of constant potential scanning. © 2011 American Chemical Society

Voltammetric sensor based on carbon paste electrode modified with molecular imprinted polymer for determination of sulfadiazine in milk and human serum.

PubMed

Sadeghi, Susan; Motaharian, Ali

2013-12-01

A new sensitive voltammetric sensor for determination of sulfadiazine is described. The developed sensor is based on carbon paste electrode modified with sulfadiazine imprinted polymer (MIP) as a recognition element. For comparison, a non-imprinted polymer (NIP) modified carbon paste electrode was prepared. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods were performed to study the binding event and electrochemical behavior of sulfadiazine at the modified carbon paste electrodes. The determination of sulfadiazine after its extraction onto the electrode surface was carried out by DPV at 0.92 V vs. Ag/AgCl owing to oxidation of sulfadiazine. Under the optimized operational conditions, the peak current obtained at the MIP modified carbon paste electrode was proportional to the sulfadiazine concentration within the range of 2.0×10(-7)-1.0×10(-4) mol L(-1) with a detection limit and sensitivity of 1.4×10(-7) mol L(-1) and 4.2×10(5) μA L mol(-1), respectively. The reproducibility of the developed sensor in terms of relative standard deviation was 2.6%. The sensor was successfully applied for determination of sulfadiazine in spiked cow milk and human serum samples with recovery values in the range of 96.7-100.9%. © 2013.

Validated electrochemical and chromatographic quantifications of some antibiotic residues in pharmaceutical industrial waste water.

PubMed

Ibrahim, Heba K; Abdel-Moety, Mona M; Abdel-Gawad, Sherif A; Al-Ghobashy, Medhat A; Kawy, Mohamed Abdel

2017-03-01

Realistic implementation of ion selective electrodes (ISEs) into environmental monitoring programs has always been a challenging task. This could be largely attributed to difficulties in validation of ISE assay results. In this study, the electrochemical response of amoxicillin trihydrate (AMX), ciprofloxacin hydrochloride (CPLX), trimethoprim (TMP), and norfloxacin (NFLX) was studied by the fabrication of sensitive membrane electrodes belonging to two types of ISEs, which are polyvinyl chloride (PVC) membrane electrodes and glassy carbon (GC) electrodes. Linear response for the membrane electrodes was in the concentration range of 10 -5 -10 -2  mol/L. For the PVC membrane electrodes, Nernstian slopes of 55.1, 56.5, 56.5, and 54.0 mV/decade were achieved over a pH 4-8 for AMX, CPLX, and NFLX, respectively, and pH 3-6 for TMP. On the other hand, for GC electrodes, Nernstian slopes of 59.1, 58.2, 57.0, and 58.2 mV/decade were achieved over pH 4-8 for AMX, CPLX, and NFLX, respectively, and pH 3-6 for TMP. In addition to assay validation to international industry standards, the fabricated electrodes were also cross-validated relative to conventional separation techniques; high performance liquid chromatography (HPLC), and thin layer chromatography (TLC)-densitometry. The HPLC assay was applied in concentration range of 0.5-10.0 μg/mL, for all target analytes. The TLC-densitometry was adopted over a concentration range of 0.3-1.0 μg/band, for AMX, and 0.1-0.9 μg/band, for CPLX, NFLX, and TMP. The proposed techniques were successfully applied for quantification of the selected drugs either in pure form or waste water samples obtained from pharmaceutical plants. The actual waste water samples were subjected to solid phase extraction (SPE) for pretreatment prior to the application of chromatographic techniques (HPLC and TLC-densitometry). On the other hand, the fabricated electrodes were successfully applied for quantification of the antibiotic residues in actual waste water samples without any pretreatment. This finding assures the suitability of the fabricated ISEs for environmental analysis.

Preparation of glucose sensors using gold nanoparticles modified diamond electrode

NASA Astrophysics Data System (ADS)

Fachrurrazie; Ivandini, T. A.; Wibowo, W.

2017-04-01

A glucose sensor was successfully developed by immobilizing glucose oxidase (GOx) at boron-doped diamond (BDD) electrodes. Prior to GOx immobilization, the BDD was modified with gold nanoparticles (AuNPs). To immobilize AuNPs, the gold surface was modified to nitrogen termination. The characterization of the electrode surface was performed using an X-ray photoelectron spectroscopy and a scanning electron microscope, while the electrochemical properties of the enzyme electrode were characterized using cyclic voltammetry. Cyclic voltammograms of the prepared electrode for D-glucose in phosphate buffer solution pH 7 showed a new reduction peak at +0.16 V. The currents of the peak were linear in the concentration range of 0.1 M to 0.9 M, indicated that the GOx-AuNP-BDD can be applied for electrochemical glucose detection.

Improved Electrochemical Detection of Zinc Ions Using Electrode Modified with Electrochemically Reduced Graphene Oxide

PubMed Central

Kudr, Jiri; Richtera, Lukas; Nejdl, Lukas; Xhaxhiu, Kledi; Vitek, Petr; Rutkay-Nedecky, Branislav; Hynek, David; Kopel, Pavel; Adam, Vojtech; Kizek, Rene

2016-01-01

Increasing urbanization and industrialization lead to the release of metals into the biosphere, which has become a serious issue for public health. In this paper, the direct electrochemical reduction of zinc ions is studied using electrochemically reduced graphene oxide (ERGO) modified glassy carbon electrode (GCE). The graphene oxide (GO) was fabricated using modified Hummers method and was electrochemically reduced on the surface of GCE by performing cyclic voltammograms from 0 to −1.5 V. The modification was optimized and properties of electrodes were determined using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The determination of Zn(II) was performed using differential pulse voltammetry technique, platinum wire as a counter electrode, and Ag/AgCl/3 M KCl reference electrode. Compared to the bare GCE the modified GCE/ERGO shows three times better electrocatalytic activity towards zinc ions, with an increase of reduction current along with a negative shift of reduction potential. Using GCE/ERGO detection limit 5 ng·mL−1 was obtained. PMID:28787832

Application of graphene oxide/lanthanum-modified carbon paste electrode for the selective determination of dopamine

NASA Astrophysics Data System (ADS)

Ye, Fengying; Feng, Chenqi; Fu, Ning; Wu, Huihui; Jiang, Jibo; Han, Sheng

2015-12-01

A home-made carbon paste electrode (CPE) was reformed by graphene oxide (GO)/lanthanum (La) complexes, and a modified electrode, called GO-La/CPE, was fabricated for the selective determination of dopamine (DA) by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Several factors affecting the electrocatalytic performance of the modified sensor were investigated. Owning to the combination of GO and La ions, the GO-La/CPE sensor exhibited large surface area, well selectivity, good repeatability and stability in the oxidation reaction of DA. At optimal conditions, the response of the GO-La/CPE electrode for determining DA was linear in the region of 0.01-0.1 μM and 0.1-400.0 μM. The limit of detection was down to 0.32 nM (S/N = 3). In addition, this modified electrode was successfully applied to the detection of DA in real urine and serum samples by using standard adding method, showing its promising application in the electroanalysis of real samples.

Molecularly imprinted electrochemical sensor based on amine group modified graphene covalently linked electrode for 4-nonylphenol detection.

PubMed

Chen, Hong-Jun; Zhang, Zhao-Hui; Cai, Rong; Chen, Xing; Liu, Yu-Nan; Rao, Wei; Yao, Shou-Zhuo

2013-10-15

In this work, an imprinted electrochemical sensor based on electrochemical reduced graphene covalently modified carbon electrode was developed for the determination of 4-nonylphenol (NP). An amine-terminated functional graphene oxide was covalently modified onto the electrode surface with diazonium salt reactions to improve the stability and reproducibility of the imprinted sensor. The electrochemical properties of each modified electrodes were investigated with differential pulse voltammetry (DPV). The electrochemical characteristic of the imprinted sensor was also investigated using electrochemical impedance spectroscopy (EIS) in detail. The response currents of the imprinted electrode exhibited a linear relationship toward 4-nonylphenol concentration ranging from 1.0 × 10(-11) to 1.0 × 10(-8) gm L(-1) with the detection limit of 3.5 × 10(-12) gm L(-1) (S/N=3). The fabricated electrochemical imprinted sensor was successfully applied to the detection of 4-nonylphenol in rain and lake water samples. Crown Copyright © 2013 Published by Elsevier B.V. All rights reserved.

Amperometric Choline Biosensor Fabricated through Electrostatic Assembly of Bienzyme/Polyelectrolyte Hybrid Layers on Carbon Nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jun; Liu, Guodong; Lin, Yuehe

2006-03-01

We report a flow injection amperometric choline biosensors based on the electrostatic assembly of an enzyme of choline oxidase (ChO) and a bi-enzyme of ChO and horseradish peroxidase (HRP) onto multi-wall carbon nanotubes (MWCNT) modified glassy carbon (GC) electrodes. These choline biosensors were fabricated by immobilization of enzymes on the negatively charged MWCNT surface through alternatively assembling a cationic polydiallydiimethylammonium chloride (PDDA) layer and an enzyme layer. Using this layer-by-layer assembling approach, bioactive nanocomposite film of a PDDA/ChO/PDDA/HRP/PDDA/CNT (ChO/HRP/CNT) and a PDDA/ChO/PDDA/ CNT (ChO/ CNT) were fabricated on GC surface, respectively. Owning to the electrocatalytic effect of carbon nanotubes, themore » measurement of faradic responses resulting from enzymatic reactions has been realized at low potential with acceptable sensitivity. It is found the ChO/HRP/CNT biosensor is more sensitive than the ChO/CNT one. Experimental parameters affecting the sensitivity of biosensors, e.g. applied potential, flow rate, etc. were optimized and potential interference was examined. The response time for this choline biosensor is fast (less than a few seconds). The linear range of detection for the choline biosensor is from 5 x 10-5 to 5 x 10-3 M and the detection limit is determined to be about 1.0 x 10-5 M.« less

Association of the macrophage activating factor (MAF) precursor activity with polymorphism in vitamin D-binding protein.

PubMed

Nagasawa, Hideko; Sasaki, Hideyuki; Uto, Yoshihiro; Kubo, Shinichi; Hori, Hitoshi

2004-01-01

Serum vitamin D-binding protein (Gc protein or DBP) is a highly expressed polymorphic protein, which is a precursor of the inflammation-primed macrophage activating factor, GcMAF, by a cascade of carbohydrate processing reactions. In order to elucidate the relationship between Gc polymorphism and GcMAF precursor activity, we estimated the phagocytic ability of three homotypes of Gc protein, Gc1F-1F, Gc1S-1S and Gc2-2, through processing of their carbohydrate moiety. We performed Gc typing of human serum samples by isoelectric focusing (IEF). Gc protein from human serum was purified by affinity chromatography with 25-hydroxyvitamin D3-sepharose. A phagocytosis assay of Gc proteins, modified using beta-glycosidase and sialidase, was carried out. The Gc1F-1F phenotype was revealed to possess Galbeta1-4GalNAc linkage by the analysis of GcMAF precursor activity using beta1-4 linkage-specific galactosidase from jack bean. The GcMAF precursor activity of the Gc1F-1F phenotype was highest among three Gc homotypes. The Gc polymorphism and carbohydrate diversity of Gc protein are significant for its pleiotropic effects.

Electroanalytical detection of pindolol: comparison of unmodified and reduced graphene oxide modified screen-printed graphite electrodes.

PubMed

Cumba, Loanda R; Smith, Jamie P; Brownson, Dale A C; Iniesta, Jesús; Metters, Jonathan P; do Carmo, Devaney R; Banks, Craig E

2015-03-07

Recent work has reported the first electroanalytical detection of pindolol using reduced graphene oxide (RGO) modified glassy carbon electrodes [S. Smarzewska and W. Ciesielski, Anal. Methods, 2014, 6, 5038] where it was reported that the use of RGO provided significant improvements in the electroanalytical signal in comparison to a bare (unmodified) glassy carbon electrode. We demonstrate, for the first time, that the electroanalytical quantification of pindolol is actually possible using bare (unmodified) screen-printed graphite electrodes (SPEs). This paper addresses the electroanalytical determination of pindolol utilising RGO modified SPEs. Surprisingly, it is found that bare (unmodified) SPEs provide superior electrochemical signatures over that of RGO modified SPEs. Consequently the electroanalytical sensing of pindolol is explored at bare unmodified SPEs where a linear range between 0.1 μM-10.0 μM is found to be possible whilst offering a limit of detection (3σ) corresponding to 0.097 μM. This provides a convenient yet analytically sensitive method for sensing pindolol. The optimised electroanalytical protocol using the unmodified SPEs, which requires no pre-treatment (electrode polishing) or electrode modification step (such as with the use of RGO), was then further applied to the determination of pindolol in urine samples. This work demonstrates that the use of RGO modified SPEs have no significant benefits when compared to the bare (unmodified) alternative and that the RGO free electrode surface can provide electro-analytically useful performances.

Construction of an electrochemical sensor based on the electrodeposition of Au-Pt nanoparticles mixtures on multi-walled carbon nanotubes film for voltammetric determination of cefotaxime.

PubMed

Shahrokhian, Saeed; Rastgar, Shokoufeh

2012-06-07

Mixtures of gold-platinum nanoparticles (Au-PtNPs) are fabricated consecutively on a multi-walled carbon nanotubes (MWNT) coated glassy carbon electrode (GCE) by the electrodeposition method. The surface morphology and nature of the hybrid film (Au-PtNPs/MWCNT) deposited on glassy carbon electrodes is characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. The modified electrode is used as a new and sensitive electrochemical sensor for the voltammetric determination of cefotaxime (CFX). The electrochemical behavior of CFX is investigated on the surface of the modified electrode using linear sweep voltammetry (LSV). The results of voltammetric studies exhibited a considerable improvement in the oxidation peak current of CFX compared to glassy carbon electrodes individually coated with MWCNT or Au-PtNPs. Under the optimized conditions, the modified electrode showed a wide linear dynamic range of 0.004-10.0 μM with a detection limit of 1.0 nM for the voltammetric determination of CFX. The modified electrode was successfully applied for the accurate determination of trace amounts of CFX in pharmaceutical and clinical preparations.

Electrochemical selective detection of dopamine on microbial carbohydrate-doped multiwall carbon nanotube-modified electrodes.

PubMed

Jin, Joon-Hyung; Cho, Eunae; Jung, Seunho

2010-03-01

Microbial carbohydrate-doped multiwall carbon nanotube (MWNT)-modified electrodes were prepared for the purpose of determining if 4-(2-aminoethyl)benzene-1,2-diol (3,4-dihydroxyphenylalanine; dopamine) exists in the presence of 0.5 mM ascorbic acid, a representative interfering agent in neurotransmitter detection. The microbial carbohydrate dopants were alpha-cyclosophorohexadecaose (alpha-C16) from Xanthomonas oryzae and cyclic-(1 --> 2)-beta-d-glucan (Cys) from Rhizobium meliloti. The cyclic voltammetric responses showed that the highest sensitivity (5.8 x 10(-3) mA cm(-2) microM(-1)) is attained with the Cys-doped MWNT-modified ultra-trace carbon electrode, and that the alpha-C16-doped MWNT-modified glassy carbon electrode displays the best selectivity to dopamine (the approximate peak potential separation is 310 mV).

Determination of caffeic acid in wine using PEDOT film modified electrode.

PubMed

Bianchini, C; Curulli, A; Pasquali, M; Zane, D

2014-08-01

A novel method using PEDOT (poly(3,4-ethylenedioxy) thiophene) modified electrode was developed for the determination of caffeic acid (CA) in wine. Cyclic voltammetry (CV) with the additions standard method was used to quantify the analyte at PEDOT modified electrodes. PEDOT films were electrodeposited on Platinum electrode (Pt) in aqueous medium by galvanostatic method using sodium poly(styrene-4-sulfonate) (PSS) as electrolyte and surfactant. CV allows detecting the analyte over a wide concentration range (10.0nmoll(-1)-6.5mmoll(-1)). The electrochemical method proposed showed good statistical and analytical parameters as linearity range, LOD, LOQ and sensitivity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrochemical behavior of adrenaline at the carbon atom wire modified electrode

NASA Astrophysics Data System (ADS)

Xue, Kuan-Hong; Liu, Jia-Mei; Wei, Ri-Bing; Chen, Shao-Peng

2006-09-01

Electrochemical behavior of adrenaline at an electrode modified by carbon atom wires (CAWs), a new material, was investigated by cyclic voltammetry combined with UV-vis spectrometry, and forced convection method. As to the electrochemical response of redox of adrenaline/adrenalinequinone couple in 0.50 M H 2SO 4, at a nitric acid treated CAW modified electrode, the anodic and cathodic peak potentials Epa and Epc shifted by 87 mV negatively and 139 mV in the positive direction, respectively, and standard heterogeneous rate constant k0 increased by 16 times compared to the corresponding bare electrode, indicating the extraordinary activity of CAWs in electrocatalysis for the process.

[Electrochemically reductive dechlorination of chloroform in aqueous medium by codeposited palladium-nickel glassy carbon as cathode].

PubMed

Sun, Zhi-Rong; Li, Bao-Hua; Hu, Xiang; Shi, Min; Peng, Yong-Zhen

2008-05-01

The electrochemical deposition behaviors of Pd-Ni bimetal on glassy carbon (GC) electrode were studied by means of cyclic voltammetry (CV) based on orthogonal experiments. CV results reveal that Pd-Ni bimetal shows larger hydrogen adsorption peak than that of single Pd or Ni. The mixture of Ni2+ and Pd2+ can get hydrogen adsorption peak of -24.83 mA at - 500 mV (vs Hg/Hg2SO4). Scanning Electron Microscope (SEM) images reveal that nickel addition changes the distributing configuration of Pd microparticles on GC. And the appearance of Pd-Ni bimetal microparticles is distinctly different from that of single Pd and single Ni microparticles. Diameter of Pd-Ni microparticle is bigger than that of Pd microparticle and smaller than that of Ni microparticle. Effects of dechlorination current and time on removal efficiency of chloroform were also studied. The removal efficiency of chloroform increases at higher dechlorination current and longer dechlorination time. It reaches 42.53% when the dechlorination current and time are 0.5 mA and 180 min respectively on Pd-Ni/GC electrode prepared at optimum conditions. It can be envisioned that the removal efficiency of chloroform would increase further at longer dechlorination time.

The influence of different modified graphene on property of DSSCs

NASA Astrophysics Data System (ADS)

Xu, Kai; Shen, Yue; Zhang, Zongkun; Cao, Meng; Gu, Feng; Wang, Linjun

2016-01-01

Two kinds of modified reduced graphene oxide (rGO) power with different hydrophilic property were synthesized in NH3/hydrazine hydrate (N-rGO) and KOH/hydrazine hydrate (K-rGO) reduction systems, respectively, and be used as counter electrode materials. The as-prepared rGO counter electrodes were confirmed as substitution for Pt counter electrode in dye-sensitized solar cells (DSSCs). The efficiency (η) of DSSCs based on N-rGO counter electrodes achieved 4.72% while that of K-rGO counter electrode was just 3.38%. The electrochemical impedance spectroscopy (EIS) measurements revealed that the hydrophilic K-rGO counter electrode has a low charge transfer resistance (Rct) and the hydrophobic N-rGO counter electrode has a low series resistance (Rs).

Application of nickel zinc ferrite/graphene nanocomposite as a modifier for fabrication of a sensitive electrochemical sensor for determination of omeprazole in real samples.

PubMed

Afkhami, Abbas; Bahiraei, Atousa; Madrakian, Tayyebeh

2017-06-01

In the present study, a simple and highly sensitive sensor for the determination of omeprazole based on nickel-zinc ferrite/graphene modified glassy carbon electrode is reported. The morphology and electro analytical performance of the fabricated sensor were characterized with X-ray diffraction spectrometry, Fourier transform infrared spectrometry, scanning electron microscopy, electrochemical impedance spectroscopy, cyclic voltammetry, differential pulse voltammetry and operation of the sensor. Results were compared with those achieved at the graphene modified glassy carbon electrode and bare glassy carbon electrode. Under the optimized experimental conditions, linear response was over the range of 0.03-100.0µmolL -1 . The lower detection limit was found to be 0.015µmolL -1 . The effect of different interferences on the anodic current response of OMZ was investigated. By measuring the concentrations of omeprazole in plasma and pharmaceutical samples, the practical application of the modified electrode was evaluated. This revealed that the nickel-zinc ferrite/graphene modified glassy carbon electrode shows excellent analytical performance for the determination of omeprazole with a very low detection limit, high sensitivity, and very good accuracy. Copyright © 2017 Elsevier Inc. All rights reserved.

Gold Electrodes Modified with Self-Assembled Monolayers for Measuring L-Ascorbic Acid: An Undergraduate Analytical Chemistry Laboratory Experiment

ERIC Educational Resources Information Center

Ito, Takashi; Perera, D. M. Neluni T.; Nagasaka, Shinobu

2008-01-01

This article describes an undergraduate electrochemistry laboratory experiment in which the students measure the L-ascorbic acid content of a real sample. Gold electrodes modified with self-assembled monolayers (SAMs) of thioctic acid and cysteamine are prepared to study the effects of surface modification on the electrode reaction of L-ascorbic…

Detection of vitamin b1 (thiamine) using modified carbon paste electrodes with polypyrrole

NASA Astrophysics Data System (ADS)

Muppariqoh, N. M.; Wahyuni, W. T.; Putra, B. R.

2017-03-01

Vitamin B1 (thiamine) is oxidized in alkaline medium and can be detected by cyclic voltammetry technique using carbon paste electrode (CPE) as a working electrode. polypyrrole-modified CPE were used in this study to increase sensitivity and selectivity measurement of thiamine. Molecularly imprinted polymers (MIP) of the modified CPE was prepared through electrodeposition of pyrrole. Measurement of thiamine performed in KCl 0.05 M (pH 10, tris buffer) using CPE and the modified CPE gave an optimum condition anodic current of thiamine at 0.3 V, potential range (-1.6_1 V), and scan rate of 100 mV/s. Measurement of thiamine using polypyrrole modified CPE (CPE-MIPpy) showed better result than CPE itself with detection limit of 6.9×10-5 M and quantitation limit 2.1×10-4 M. CPE-MIPpy is selective to vita min B1. In conclusion, CPE-MIPpy as a working electrode showed better performance of thiamine measurement than that of CPE.

Design, Synthesis, and Use of Peptides Derived from Human Papillomavirus L1 Protein for the Modification of Gold Electrode Surfaces by Self-Assembled Monolayers.

PubMed

Lara Carrillo, John Alejandro; Fierro Medina, Ricardo; Manríquez Rocha, Juan; Bustos Bustos, Erika; Insuasty Cepeda, Diego Sebastián; García Castañeda, Javier Eduardo; Rivera Monroy, Zuly Jenny

2017-11-14

In order to obtain gold electrode surfaces modified with Human Papillomavirus L1 protein (HPV L1)-derived peptides, two sequences, SPINNTKPHEAR and YIK, were chosen. Both have been recognized by means of sera from patients infected with HPV. The molecules, Fc-Ahx-SPINNTKPHEAR, Ac-C- Ahx -(Fc)KSPINNTKPHEAR, Ac-C- Ahx -SPINNTKPHEAR(Fc)K, C- Ahx -SPINNTKPHEAR, and (YIK)₂- Ahx -C, were designed, synthesized, and characterized. Our results suggest that peptides derived from the SPINNTKPHEAR sequence, containing ferrocene and cysteine residues, are not stable and not adequate for electrode surface modification. The surface of polycrystalline gold electrodes was modified with the peptides C-Ahx-SPINNTKPHEAR or (YIK)₂-Ahx-C through self-assembly. The modified polycrystalline gold electrodes were characterized via infrared spectroscopy and electrochemical measurements. The thermodynamic parameters, surface coverage factor, and medium pH effect were determined for these surfaces. The results indicate that surface modification depends on the peptide sequence (length, amino acid composition, polyvalence, etc.). The influence of antipeptide antibodies on the voltammetric response of the modified electrode was evaluated by comparing results obtained with pre-immune and post-immune serum samples.

An electrochemically-driven dual-mode display device with both reflective and emissive modes using poly(p-phenylenevinylene) derivatives

NASA Astrophysics Data System (ADS)

Tsuneyasu, Shota; Jin, Lu; Nakamura, Kazuki; Kobayashi, Norihisa

2016-04-01

We demonstrate a novel electrochemical dual-mode displaying (DMD) device, which enables control of both coloration and light emission using an electrochemical reaction. The coloration control of the DMD device was based on an electrochromic (EC) reaction, whereas the light emission of the device was caused by an electrochemiluminescence (ECL) mechanism. This novel DMD device consisted of a pair of facing conductive polymer-modified electrodes: comb-shaped interdigitated Au electrodes modified with poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) layers and poly(2,3-dihydrothieno-1,4-dioxin)-poly(styrene sulfonate) (PEDOT/PSS) film-modified indium tin oxide (ITO) electrodes. When a bias voltage was applied between the PEDOT/PSS film-modified ITO electrode and the comb-shaped electrodes, a color change of the device was observed by the EC reaction of the MEH-PPV and PEDOT/PSS. On the other hand, an emission was obtained when the bias voltage was applied between two comb-shaped interdigitated electrodes. The orange emission was ascribed to the ECL reaction of the MEH-PPV layer, which resulted from the formation of a p-i-n junction in this layer.

Characterization of modified SiC@SiO2 nanocables/MnO2 and their potential application as hybrid electrodes for supercapacitors.

PubMed

Zhang, Yujie; Chen, Junhong; Fan, Huili; Chou, Kuo-Chih; Hou, Xinmei

2015-12-14

In this research, we demonstrate a simple route for preparing SiC@SiO2 core-shell nanocables and furthermore obtain SiC@SiO2 nanocables/MnO2 as hybrid electrodes for supercapacitors using various modified methods. The modified procedure consists of mild modifications using sodium hydroxide as well as UV light irradiation and deposition of MnO2. The morphology and microstructural characteristics of the composites are investigated using XRD, XPS, FE-SEM with EDS and TEM. The results indicate that the surfaces of modified SiC@SiO2 nanocables are uniformly coated with a MnO2 thin layer. The electrochemical behaviors of the hybrid electrodes are systematically measured in a three-electrode system using cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. The resultant electrode presents a superb charge storage characteristic with a large specific capacitance of 276.3 F g(-1) at the current density of 0.2 A g(-1). Moreover, the hybrid electrode also displays a long cycle life with a good capacitance retention (∼92.0%) after 1000 CV cycles, exhibiting a promising potential for supercapacitors.

Satisfactory surgical outcome of T2 gastric cancer after modified D2 lymphadenectomy.

PubMed

Zhang, Shupeng; Wu, Liangliang; Wang, Xiaona; Ding, Xuewei; Liang, Han

2017-04-01

Though D2 lymphadenectomy has been increasingly regarded as standard surgical procedure for advanced gastric cancer (GC), the modified D2 (D1 + 7, 8a and 9) lymphadenectomy may be more suitable than D2 dissection for T2 stage GC. The purpose of this study is to elucidate whether the surgical outcome of modified D2 lymphadenectomy was comparable to that of standard D2 dissection in T2 stage GC patients. A retrospective cohort study with 77 cases and 77 controls matched for baseline characteristics was conducted. Patients were categorized into two groups according to the extent of lymphadenectomy: the modified D2 group (mD2) and the standard D2 group (D2). Surgical outcome and recurrence date were compared between the two groups. The 5-year overall survival (OS) rate was 71.4% for patients accepted mD2 lymphadenectomy and 70.1% for those accepted standard D2, respectively, and the difference was not statistically significant. Multivariate survival analysis revealed that curability, tumor size, TNM stage and postoperative complications were independently prognostic factors for T2 stage GC patients. Patients in the mD2 group tended to have less intraoperative blood loss (P=0.001) and shorter operation time (P<0.001) than those in the D2 group. While there were no significant differences in recurrence rate and types, especially lymph node recurrence, between the two groups. The surgical outcome of mD2 lymphadenectomy was equal to that of standard D2, and the use of mD2 instead of standard D2 can be a better option for T2 stage GC.

Green synthesis of gold nanoparticles for trace level detection of a hazardous pollutant (nitrobenzene) causing Methemoglobinaemia.

PubMed

Emmanuel, R; Karuppiah, Chelladurai; Chen, Shen-Ming; Palanisamy, Selvakumar; Padmavathy, S; Prakash, P

2014-08-30

The present study involves a green synthesis of gold nanoparticles (Au-NPs) using Acacia nilotica twig bark extract at room temperature and trace level detection of one of the hazardous materials, viz. nitrobenzene (NB) that causes Methemoglobinaemia. The synthesis protocol demonstrates that the bioreduction of chloroauric acid leads to the formation of Au-NPs within 10min, suggesting a higher reaction rate than any other chemical methods involved. The obtained Au-NPs have been characterized by UV-vis spectroscopy, X-ray diffraction, transmission electron microscopy, Energy-Dispersive X-ray Spectroscopy and Fourier Transform Infrared Spectroscopy. The electrochemical detection of NB has been investigated at the green synthesized Au-NPs modified glassy carbon electrode by using differential pulse voltammetry (DPV). The Au-NPs modified electrode exhibits excellent reduction ability toward NB compared to unmodified electrode. The developed NB sensor at Au-NPs modified electrode displays a wide linear response from 0.1 to 600μM with high sensitivity of 1.01μAμM(-1)cm(-2) and low limit of detection of 0.016μM. The modified electrode shows exceptional selectivity in the presence of ions, phenolic and biologically coactive compounds. In addition, the Au-NPs modified electrode exhibits an outstanding recovery results toward NB in various real water samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Study the effect of active carbon modified using HNO3 for carbon electrodes in capacitive deionization system

NASA Astrophysics Data System (ADS)

Blegur, Ernes Josias; Endarko

2017-01-01

Carbon electrodes prepared with crosslink method for desalination purpose has been synthesized and characterized. The carbon electrodes were synthesized with activated carbon (700 - 1400 m2/g) and polyvinyl alcohol (PVA) as a binder using crosslink method with temperature crosslink at 120°C. Electrochemical properties of carbon electrodes were examined using electrical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The proposed study was to measure the salt-removal percentage of 330 µS/cm NaCl using a capacitive deionization (CDI) unit cell prepared with two pairs of carbon electrodes. The applied potential of 2.0 V and a flow rate of 25 mL/min were used to desalination tests. The result showed that the greatest value of the percentage of salt-removal was achieved at 36.1% for the carbon electrodes with Active Carbon Modified (ACM) while the salt-removal percentage for the Active Carbon (AC) electrodes only at 22%. The fact indicates that the active carbon modified using HNO3 can improve the efficiency of CDI about 14%.

Direct electrochemistry of Shewanella loihica PV-4 on gold nanoparticles-modified boron-doped diamond electrodes fabricated by layer-by-layer technique.

PubMed

Wu, Wenguo; Xie, Ronggang; Bai, Linling; Tang, Zuming; Gu, Zhongze

2012-05-01

Microbial Fuel Cells (MFCs) are robust devices capable of taping biological energy, converting pollutants into electricity through renewable biomass. The fabrication of nanostructured electrodes with good bio- and electrochemical activity, play a profound role in promoting power generation of MFCs. Au nanoparticles (AuNPs)-modified Boron-Doped Diamond (BDD) electrodes are fabricated by layer-by-layer (LBL) self-assembly technique and used for the direct electrochemistry of Shewanella loihica PV-4 in an electrochemical cell. Experimental results show that the peak current densities generated on the Au/PAH multilayer-modified BDD electrodes increased from 1.25 to 2.93 microA/cm(-2) as the layer increased from 0 to 6. Different cell morphologies of S. loihica PV-4 were also observed on the electrodes and the highest density of cells was attached on the (Au/PAH)6/BDD electrode with well-formed three-dimensional nanostructure. The electrochemistry of S. loihica PV-4 was enhanced on the (Au/PAH)4/BDD electrode due to the appropriate amount of AuNPsand thickness of PAH layer.

Poly(dimethylsiloxane) cross-linked carbon paste electrodes for microfluidic electrochemical sensing.

PubMed

Sameenoi, Yupaporn; Mensack, Meghan M; Boonsong, Kanokporn; Ewing, Rebecca; Dungchai, Wijitar; Chailapakul, Orawan; Cropek, Donald M; Henry, Charles S

2011-08-07

Recently, the development of electrochemical biosensors as part of microfluidic devices has garnered a great deal of attention because of the small instrument size and portability afforded by the integration of electrochemistry in microfluidic systems. Electrode fabrication, however, has proven to be a major obstacle in the field. Here, an alternative method to create integrated, low cost, robust, patternable carbon paste electrodes (CPEs) for microfluidic devices is presented. The new CPEs are composed of graphite powder and a binder consisting of a mixture of poly(dimethylsiloxane) (PDMS) and mineral oil. The electrodes are made by filling channels molded in previously cross-linked PDMS using a method analogous to screen printing. The optimal binder composition was investigated to obtain electrodes that were physically robust and performed well electrochemically. After studying the basic electrochemistry, the PDMS-oil CPEs were modified with multi-walled carbon nanotubes (MWCNT) and cobalt phthalocyanine (CoPC) for the detection of catecholamines and thiols, respectively, to demonstrate the ease of electrode chemical modification. Significant improvement of analyte signal detection was observed from both types of modified CPEs. A nearly 2-fold improvement in the electrochemical signal for 100 μM dithiothreitol (DTT) was observed when using a CoPC modified electrode (4.0 ± 0.2 nA (n = 3) versus 2.5 ± 0.2 nA (n = 3)). The improvement in signal was even more pronounced when looking at catecholamines, namely dopamine, using MWCNT modified CPEs. In this case, an order of magnitude improvement in limit of detection was observed for dopamine when using the MWCNT modified CPEs (50 nM versus 500 nM). CoPC modified CPEs were successfully used to detect thiols in red blood cell lysate while MWCNT modified CPEs were used to monitor temporal changes in catecholamine release from PC12 cells following stimulation with potassium.

Highly selective dopamine electrochemical sensor based on electrochemically pretreated graphite and nafion composite modified screen printed carbon electrode.

PubMed

Ku, Shuhao; Palanisamy, Selvakumar; Chen, Shen-Ming

2013-12-01

Herein, we report a highly selective dopamine electrochemical sensor based on electrochemically pretreated graphite/nafion composite modified screen printed carbon (SPC) electrode. Electrochemically activated graphite/nafion composite was prepared by using a simple electrochemical method. Scanning electron microscope (SEM) used to characterize the surface morphology of the fabricated composite electrode. The SEM result clearly indicates that the graphitic basal planes were totally disturbed and leads to the formation of graphite nanosheets. The composite modified electrode showed an enhanced electrocatalytic activity toward the oxidation of DA when compared with either electrochemical pretreated graphite or nafion SPC electrodes. The fabricated composite electrode exhibits a good electrocatalytic oxidation toward DA in the linear response range from 0.5 to 70 μM with the detection limit of 0.023 μM. The proposed sensor also exhibits very good selectivity and stability, with the appreciable sensitivity. In addition, the proposed sensor showed satisfactory recovery results toward the commercial pharmaceutical DA samples. Copyright © 2013 Elsevier Inc. All rights reserved.

Monolithic quasi-solid-state dye-sensitized solar cells based on graphene-modified mesoscopic carbon-counter electrodes

NASA Astrophysics Data System (ADS)

Rong, Yaoguang; Han, Hongwei

2013-01-01

A monolithic quasi-solid-state dye-sensitized solar cell (DSSC) based on graphene-modified mesoscopic carbon-counter electrode is developed. A TiO2-working electrode layer, ZrO2 spacer layer, and carbon counter electrode layer were constructed on a single conducting glass substrate by screen printing. The quasi-solid-state polymer gel electrolyte employed a polymer composite as the gelator, and effectively infiltrated the porous layers. Fabricated with normal carbon-counter electrode (NC-CE) containing graphite and carbon black, the DSSC had a power conversion efficiency (PCE) of 5.09% with the fill factor of 0.63 at 100 mW cm-2 AM1.5 illumination. When the NC-CE was modified with graphene sheets, the PCE and fill factor were enhanced to 6.27% and 0.71, respectively. This improvement indicates excellent conductivity and high electrocatalytic activity of the graphene sheets, which have been considered as a promising platinum-free electrode material for DSSCs.

Cloud Point Extraction for Electroanalysis: Anodic Stripping Voltammetry of Cadmium

PubMed Central

Rusinek, Cory A.; Bange, Adam; Papautsky, Ian; Heineman, William R.

2016-01-01

Cloud point extraction (CPE) is a well-established technique for the pre-concentration of hydrophobic species from water without the use of organic solvents. Subsequent analysis is then typically performed via atomic absorption spectroscopy (AAS), UV-Vis spectroscopy, or high performance liquid chromatography (HPLC). However, the suitability of CPE for electroanalytical methods such as stripping voltammetry has not been reported. We demonstrate the use of CPE for electroanalysis using the determination of cadmium (Cd2+) by anodic stripping voltammetry (ASV) as a representative example. Rather than using the chelating agents which are commonly used in CPE to form a hydrophobic, extractable metal complex, we used iodide and sulfuric acid to neutralize the charge on Cd2+ to form an extractable ion pair. Triton X-114 was chosen as the surfactant for the extraction because its cloud point temperature is near room temperature (22–25° C). Bare glassy carbon (GC), bismuth-coated glassy carbon (Bi-GC), and mercury-coated glassy carbon (Hg-GC) electrodes were compared for the CPE-ASV. A detection limit for Cd2+ of 1.7 nM (0.2 ppb) was obtained with the Hg-GC electrode. Comparison of ASV analysis without CPE was also investigated and a 20x decrease (4.0 ppb) in the detection limit was observed. The suitability of this procedure for the analysis of tap and river water samples was also demonstrated. This simple, versatile, environmentally friendly and cost-effective extraction method is potentially applicable to a wide variety of transition metals and organic compounds that are amenable to detection by electroanalytical methods. PMID:25996561

The Simultaneous Electrochemical Detection of Catechol and Hydroquinone with [Cu(Sal-β-Ala)(3,5-DMPz)2]/SWCNTs/GCE

PubMed Central

Alshahrani, Lina Abdullah; Li, Xi; Luo, Hui; Yang, Linlin; Wang, Mengmeng; Yan, Songling; Liu, Peng; Yang, Yuqin; Li, Quanhua

2014-01-01

A glassy carbon electrode was modified with a copper(II) complex [Cu(Sal-β-Ala) (3,5-DMPz)2] (Sal = salicylaldehyde, β-Ala = β-alanine, 3,5-DMPz = 3,5-dimethylpyrazole) and single-walled carbon nanotubes (SWCNTs). The modified electrode was used to detect catechol (CT) and hydroquinone (HQ) and exhibited good electrocatalytic activities toward the oxidation of CT and HQ. The peak currents were linear with the CT and HQ concentrations over the range of 5–215 μmol·L−1 and 5–370 μmol·L−1 with corresponding detection limits of 3.5 μmol·L−1 and 1.46 μmol·L−1 (S/N = 3) respectively. Moreover, the modified electrode exhibited good sensitivity, stability and reproducibility for the determination of CT and HQ, indicating the promising applications of the modified electrode in real sample analysis. PMID:25429411

Investigation of the Ionization Mechanism of NAD+/NADH-Modified Gold Electrodes in ToF-SIMS Analysis.

PubMed

Hua, Xin; Zhao, Li-Jun; Long, Yi-Tao

2018-06-04

Analysis of nicotinamide adenine dinucleotide (NAD + /NADH)-modified electrodes is important for in vitro monitoring of key biological processes. In this work, time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to analyze NAD + /NADH-modified gold electrodes. Interestingly, no obvious characteristic peaks of nicotinamide fragment could be observed in the mass spectra of NAD + /NADH in their neutral sodium pyrophosphate form. However, after acidification, the characteristic peaks for both NAD + and NADH were detected. This was due to the suppression effect of inner pyrophosphoric salts in both neutral molecules. Besides, it was proved that the suppression by inner salt was intramolecular. No obvious suppression was found between neighboring molecules. These results demonstrated the suppression effect of inner salts in ToF-SIMS analysis, providing useful evidence for the study of ToF-SIMS ionization mechanism of organic molecule-modified electrodes. Graphical Abstract ᅟ.

In situ Observation of Direct Electron Transfer Reaction of Cytochrome c Immobilized on ITO Electrode Modified with 11-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}undecylphosphonic Acid Self-assembled Monolayer Film by Electrochemical Slab Optical Waveguide Spectroscopy.

PubMed

Matsuda, Naoki; Okabe, Hirotaka; Omura, Ayako; Nakano, Miki; Miyake, Koji

2017-01-01

To immobilize cytochrome c (cyt.c) on an ITO electrode while keeping its direct electron transfer (DET) functionality, the ITO electrode surface was modified with 11-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}undecylphosphonic acid (CH 3 O (CH 2 CH 2 O) 3 C 11 H 22 PO(OH) 2 , M-EG 3 -UPA) self-assembled monolayer (SAM) film. After a 100-times washing process to exchange a phosphate buffer saline solution surrounding cyt.c and ITO electrode to a fresh one, an in situ observation of visible absorption spectral change with slab optical waveguide (SOWG) spectroscopy showed that 87.7% of the cyt.c adsorbed on the M-EG 3 -UPA modified ITO electrode remained on the ITO electrode. The SOWG absorption spectra corresponding to oxidized and reduced cyt.c were observed with setting the ITO electrode potential at 0.3 and -0.3 V vs. Ag/AgCl, respectively, while probing the DET reaction between cyt.c and ITO electrode occurred. The amount of cyt.c was evaluated to be about 19.4% of a monolayer coverage based on the coulomb amount in oxidation and reduction peaks on cyclic voltammetry (CV) data. The CV peak current maintained to be 83.4% compared with the initial value for a M-EG 3 -UPA modified ITO electrode after 60 min continuous scan with 0.1 V/s between 0.3 and -0.3 V vs. Ag/AgCl.

Effective Electrochemistry of Human Sulfite Oxidase Immobilized on Quantum-Dots-Modified Indium Tin Oxide Electrode.

PubMed

Zeng, Ting; Leimkühler, Silke; Koetz, Joachim; Wollenberger, Ulla

2015-09-30

The bioelectrocatalytic sulfite oxidation by human sulfite oxidase (hSO) on indium tin oxide (ITO) is reported, which is facilitated by functionalizing of the electrode surface with polyethylenimine (PEI)-entrapped CdS nanoparticles and enzyme. hSO was assembled onto the electrode with a high surface loading of electroactive enzyme. In the presence of sulfite but without additional mediators, a high bioelectrocatalytic current was generated. Reference experiments with only PEI showed direct electron transfer and catalytic activity of hSO, but these were less pronounced. The application of the polyelectrolyte-entrapped quantum dots (QDs) on ITO electrodes provides a compatible surface for enzyme binding with promotion of electron transfer. Variations of the buffer solution conditions, e.g., ionic strength, pH, viscosity, and the effect of oxygen, were studied in order to understand intramolecular and heterogeneous electron transfer from hSO to the electrode. The results are consistent with a model derived for the enzyme by using flash photolysis in solution and spectroelectrochemistry and molecular dynamic simulations of hSO on monolayer-modified gold electrodes. Moreover, for the first time a photoelectrochemical electrode involving immobilized hSO is demonstrated where photoexcitation of the CdS/hSO-modified electrode lead to an enhanced generation of bioelectrocatalytic currents upon sulfite addition. Oxidation starts already at the redox potential of the electron transfer domain of hSO and is greatly increased by application of a small overpotential to the CdS/hSO-modified ITO.

Synthesis and electrochemical detection of a thiazolyl-indole natural product isolated from the nosocomial pathogen Pseudomonas aeruginosa.

PubMed

Buzid, Alyah; Muimhneacháin, Eoin Ó; Reen, F Jerry; Hayes, Phyllis E; Pardo, Leticia M; Shang, Fengjun; O'Gara, Fergal; Sperry, Jonathan; Luong, John H T; Glennon, Jeremy D; McGlacken, Gerard P

2016-09-01

Pseudomonas aeruginosa is a Gram-negative opportunistic pathogen, capable of surviving in a broad range of natural environments and quickly acquiring resistance. It is associated with hospital-acquired infections, particularly in patients with compromised immunity, and is the primary cause of morbidity and mortality in cystic fibrosis (CF) patients. P. aeruginosa is also of nosocomial importance on dairy farms and veterinary hospitals, where it is a key morbidity factor in bovine mastitis. P. aeruginosa uses a cell-cell communication system consisting of signalling molecules to coordinate bacterial secondary metabolites, biofilm formation, and virulence. Simple and sensitive methods for the detection of biomolecules as indicators of P. aeruginosa infection would be of great clinical importance. Here, we report the synthesis of the P. aeruginosa natural product, barakacin, which was recently isolated from the bovine ruminal strain ZIO. A simple and sensitive electrochemical method was used for barakacin detection using a boron-doped diamond (BDD) and glassy carbon (GC) electrodes, based on cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The influence of electrolyte pH on the peak potential and peak currents was also investigated. At pH 2.0, the peak current was linearly dependent on barakacin concentration (in the range used, 1-10 μM), with correlation coefficients greater than 0.98 on both electrodes. The detection limit (S/N = 3) on the BDD electrode was 100-fold lower than that obtained on the GC electrode. The optimized method using the BDD electrode was extended to bovine (cow feces) and human (sputum of a CF patient) samples. Spiked barakacin was easily detected in these matrices at a limit of 0.5 and 0.05 μM, respectively. Graphical abstract Electrochemical detection of barakacin.

Electrochemical sensing of bisphenol using a multilayer graphene nanobelt modified photolithography patterned platinum electrode

NASA Astrophysics Data System (ADS)

Karthick Kannan, Padmanathan; Hu, Chunxiao; Morgan, Hywel; Moshkalev, Stanislav A.; Sekhar Rout, Chandra

2016-09-01

An electrochemical sensor has been developed for the detection of Bisphenol-A (BPA) using photolithographically patterned platinum electrodes modified with multilayer graphene nanobelts (GNB). Compared to bare electrodes, the GNB modified electrode exhibited enhanced BPA oxidation current, due to the high effective surface area and high adsorption capacity of the GNB. The sensor showed a linear response over the concentration range from 0.5 μM-9 μM with a very low limit of detection = 37.33 nM. In addition, the sensor showed very good stability and reproducibility with good specificity, demonstrating that GNB is potentially a new material for the development of a practical BPA electrochemical sensor with application in both industrial and plastic industries.

Application of Carbon-Microsphere-Modified Electrodes for Electrochemistry of Hemoglobin and Electrocatalytic Sensing of Trichloroacetic Acid

PubMed Central

Wang, Wen-Cheng; Yan, Li-Jun; Shi, Fan; Niu, Xue-Liang; Huang, Guo-Lei; Zheng, Cai-Juan; Sun, Wei

2015-01-01

By using the hydrothermal method, carbon microspheres (CMS) were fabricated and used for electrode modification. The characteristics of CMS were investigated using various techniques. The biocompatible sensing platform was built by immobilizing hemoglobin (Hb) on the micrometer-sized CMS-modified electrode with a layer of chitosan membrane. On the cyclic voltammogram, a couple of quasi-reversible cathodic and anodic peaks appeared, showing that direct electrochemistry of Hb with the working electrode was achieved. The catalytic reduction peak currents of the bioelectrode to trichloroacetic acid was established in the linear range of 2.0~70.0 mmol·L−1 accompanied by a detection limit of 0.30 mmol·L−1 (3σ). The modified electrode displayed favorable sensitivity, good reproducibility and stability, which suggests that CMS is promising for fabricating third-generation bioelectrochemical sensors. PMID:26703621

Intensification of electrochemiluminescence of luminol on TiO2 supported Au atomic cluster nano-hybrid modified electrode.

PubMed

Yu, Zhimin; Wei, Xiuhua; Yan, Jilin; Tu, Yifeng

2012-04-21

With TiO(2) nanoparticles as carrier, a supported nano-material of Au atomic cluster/TiO(2) nano-hybrid was synthesized. It was then modified onto the surface of indium tin oxide (ITO) by Nafion to act as a working electrode for exciting the electrochemiluminescence (ECL) of luminol. The properties of the nano-hybrid and the modified electrode were characterized by XRD, XPS, electronic microscopy, electrochemistry and spectroscopy. The experimental results demonstrated that the modification of this nano-hybrid onto the ITO electrode efficiently intensified the ECL of luminol. It was also revealed that the ECL intensity of luminol on this modified electrode showed very sensitive responses to oxygen and hydrogen peroxide. The detection limits for dissolved oxygen and hydrogen peroxide were 2 μg L(-1) and 5.5 × 10(-12) M, respectively. Besides the discussion of the intensifying mechanism of this nano-hybrid for ECL of luminol, the developed method was also applied for monitoring dissolved oxygen and evaluating the scavenging efficiency of reactive oxygen species of the Ganoderma lucidum spore.

A new modification method of a Cetyl Trimethyl Ammonium Bromide/Nano-ZnO and Multi-walled Carbon Nanotubes Electrode for Determination of Anti Doping in Urine

NASA Astrophysics Data System (ADS)

Zhao, Zhiwei; Mu, Shuai; Zheng, Jie; Gu, Lingyan; Shen, Guijun; Shen, Yuan

2017-07-01

The preparation and application of Cetyl Trimethyl Ammonium Bromide/Nano-ZnO and Multi-walled Carbon Nanotubes (CTAB/ZnO-MWNTs) Modified Electrodes was studied, establishing a new electrochemical method for determination of carteolol hydrochloride in urine. After its pre-enrichment by adsorption and extraction on modified electrodes, electrochemical behaviors of carteolol hydrochloride on the modified electrodes were studied by CV and DPV. The response is linear at the range of 1×10-3 ∼ 2×10-1 g/L, with a detection limit of 2×10-4 g/L. Under appropriate conditions, the content of carteolol hydrochloride in urine can be determined directly by the method, which had strong anti-interference ability and the recovery is 96.5% - 110.5%. In addition, extraction and adsorption behaviors of the modified electrodes for carteolol hydrochloride were studied by chronocoulumetry, and the results showed that extraction during the enrichment process played a major role at low concentrations, and contribution of surface adsorption became greater with the increase of concentrations.

Voltammetric Sensor Based on Fe-doped ZnO and TiO2 Nanostructures-modified Carbon-paste Electrode for Determination of Levodopa

NASA Astrophysics Data System (ADS)

Anaraki Firooz, Azam; Hosseini Nia, Bahram; Beheshtian, Javad; Ghalkhani, Masoumeh

2017-10-01

In this study, undoped and 1 wt.% Fe-doped with ZnO, and TiO2 nanostructures were synthesized by a simple hydrothermal method without using templates. The influence of the Fe dopant on structural, optical and electrochemical response was studied by x-ray diffraction, scanning electron microscopy, UV-Vis spectra, photoluminescence spectra and electrochemical characterization system. The electrochemical response of the carbon paste electrode modified with synthesized nanostructures (undoped ZnO and TiO2 as well as doped with Fe ions) toward levodopa (L-Dopa) was studied. Cyclic voltammetry using provided modified electrodes showed electro-catalytic properties for electro-oxidation of L-Dopa and a significant reduction was observed in the anodic overvoltage compared to the bare electrode. The results indicated the presence of the sufficient dopants. The best response was obtained in terms of the current enhancement, overvoltage reduction, and reversibility improvement of the L-Dopa oxidation reaction under experimental conditions by the modified electrode with TiO2 nanoparticles doped with Fe ions.

Tracking metal ions with polypyrrole thin films adhesively bonded to diazonium-modified flexible ITO electrodes.

PubMed

Lo, Momath; Diaw, Abdou K D; Gningue-Sall, Diariatou; Aaron, Jean-Jacques; Oturan, Mehmet A; Chehimi, Mohamed M

2018-05-09

Adhesively bonded polypyrrole thin films doped with benzene sulfonic acid (BSA) were electrodeposited on aminobenzenediazonium-modified flexible ITO electrodes and further employed for the detection of Pb 2+ , Cu 2+ , and Cd 2+ metal ions in aqueous medium. The aminophenyl (AP) adhesive layer was grafted to ITO by electroreduction of the in situ generated parent diazonium compound. Polypyrrole (PPy) thin films exhibited remarkable adhesion to aminophenyl (ITO-AP). The strongly adherent polypyrrole films exhibited excellent electroactivity in the doped state with BSA which itself served to chelate the metal ions in aqueous medium. The surface of the resulting, modified flexible electrode was characterized by XPS, SEM, and electrochemical methods. The ITO-AP-PPy electrodes were then used for the simultaneous detection of Cu 2+ , Cd 2+ , and Pb 2+ by differential pulse voltammetry (DPV). The detection limits were 11.1, 8.95, and 0.99 nM for Cu 2+ , Cd 2+ , and Pb 2+ , respectively. In addition, the modified electrodes displayed a good reproducibility, making them suitable for the determination of heavy metals in real wastewater samples.

Highly active, bi-functional and metal-free B4C-nanoparticle-modified graphite felt electrodes for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Jiang, H. R.; Shyy, W.; Wu, M. C.; Wei, L.; Zhao, T. S.

2017-10-01

The potential of B4C as a metal-free catalyst for vanadium redox reactions is investigated by first-principles calculations. Results show that the central carbon atom of B4C can act as a highly active reaction site for redox reactions, due primarily to the abundant unpaired electrons around it. The catalytic effect is then verified experimentally by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests, both of which demonstrate that B4C nanoparticles can enhance the kinetics for both V2+/V3+ and VO2+/VO2+ redox reactions, indicating a bi-functional effect. The B4C-nanoparticle-modified graphite felt electrodes are finally prepared and tested in vanadium redox flow batteries (VRFBs). It is shown that the batteries with the prepared electrodes exhibit energy efficiencies of 88.9% and 80.0% at the current densities of 80 and 160 mA cm-2, which are 16.6% and 18.8% higher than those with the original graphite felt electrodes. With a further increase in current densities to 240 and 320 mA cm-2, the batteries can still maintain energy efficiencies of 72.0% and 63.8%, respectively. All these results show that the B4C-nanoparticle-modified graphite felt electrode outperforms existing metal-free catalyst modified electrodes, and thus can be promising electrodes for VRFBs.

Nafion/lead nitroprusside nanoparticles modified carbon ceramic electrode as a novel amperometric sensor for L-cysteine.

PubMed

Razmi, H; Heidari, H

2009-05-01

This work describes the electrochemical and electrocatalytic properties of carbon ceramic electrode (CCE) modified with lead nitroprusside (PbNP) nanoparticles as a new electrocatalyst material. The structure of deposited film on the CCE was characterized by energy dispersive X-ray (EDX), Fourier transform infrared (FTIR), and scanning electron microscopy (SEM). The cyclic voltammogram (CV) of the PbNP modified CCE showed two well-defined redox couples due to [Fe(CN)5NO](3-)/[Fe(CN)5NO](2-) and Pb(IV)/Pb(II) redox reactions. The modified electrode showed electrocatalytic activity toward the oxidation of L-cysteine and was used as an amperometric sensor. Also, to reduce the fouling effect of L-cysteine and its oxidation products on the modified electrode, a thin film of Nafion was coated on the electrode surface. The sensor response was linearly changed with L-cysteine concentration in the range of 1 x 10(-6) to 6.72 x 10(-5)mol L(-1) with a detection limit (signal/noise ratio [S/N]=3) of 0.46 microM. The sensor sensitivity was 0.17 microA (microM)(-1), and some important advantages such as simple preparation, fast response, good stability, interference-free signals, antifouling properties, and reproducibility of the sensor for amperometric determination of L-cysteine were achieved.

The natural diatomite from caldiran-van (Turkey): electroanalytical application to antimigraine compound naratriptan at modified carbon paste electrode.

PubMed

Calışkan, Necla; Sögüt, Eda; Saka, Cafer; Yardım, Yavuz; Sentürk, Zuhre

2010-09-01

This paper is the first report describing the characterization of local diatomite of Caldiran-Van region (Eastern Anatolia, Turkey). Special attention was paid to the ability of its electroanalytical performance at modified electrodes and to the potential application of diatomite-modified electrode. For this purpose, the determination of Naratriptan which is a novel oral triptan (5-hydroxytryptamine receptor agonist) in migraine treatment, by means of a carbon paste electrode modified with 10% (w/w) of diatomite was studied using cyclic and square-wave voltammetry. The experimental conditions that affect the electrode reaction process were studied in terms of pH of the supporting electrolyte, scan rate, accumulation variables, modifier composition and square-wave parameters. Using square-wave stripping mode, the drug yielded a well-defined voltammetric response in Britton-Robinson buffer, pH 4.0 at 0.84 V (vs. Ag/AgCl) (a pre-concentration step being carried out with an open circuit at 120 s). The process could be used to determine Naratriptan concentrations in the range 5x10(-7)-9x10(-7) M, with a detection limit of 1.25x10(-7) M (46.5 mug L(-1)). The applicability of the method to spiked human urine samples was illustrated.

The Analysis of Cyanide and Its Breakdown Products in Biological Samples

DTIC Science & Technology

2010-01-01

simultaneous GC-mass spectrometric (MS) analysis of cyanide and thiocyanate, and Funazo et al. (53) quantita- tively methylated cyanide and thiocyanate for...selective membrane electrode for thiocyanate ion based on a bis-taurine- salicylic binuclear copper(II) complex as ionophore. Chinese Journal of Chemistry

Carbon dots-decorated multiwalled carbon nanotubes nanocomposites as a high-performance electrochemical sensor for detection of H2O2 in living cells.

PubMed

Bai, Jing; Sun, Chunhe; Jiang, Xiue

2016-07-01

A novel enzyme-free hydrogen peroxide sensor composed of carbon dots (CDs) and multi-walled carbon nanotubes (MWCNTs) was prepared. It was found that the carbon dots-decorated multi-walled carbon nanotubes nanocomposites (CDs/MWCNTs) modified glassy carbon (GC) electrode (CDs/MWCNTs/GCE) exhibited a significant synergistic electrocatalytic activity towards hydrogen peroxide reduction as compared to carbon dots or multi-walled carbon nanotubes alone, and the CDs/MWCNTs/GCE has shown a low detection limit as well as excellent stability, selectivity, and reproducibility. These remarkable analytical advantages enable the practical application of CDs/MWCNTs/GCE for the real-time tracking of hydrogen peroxide (H2O2) released from human cervical cancer cells with satisfactory results. The enhanced electrochemical activity can be assigned to the edge plane-like defective sites and lattice oxygen in the CDs/MWCNTs nanocomposites due to the small amount of decoration of carbon dots on the multi-walled carbon nanotubes. Based on a facile preparation method and with good electrochemical properties, the CDs/MWCNTs nanocomposites represent a new class of carbon electrode for electrochemical sensor applications. Graphical Abstract CDs/MWCNTs exhibited good electrocatalytic activity and stability to H2O2 reduction and can be used for real-time detection of H2O2 released from living cells.

Fabrication of sensitive enzymatic biosensor based on multi-layered reduced graphene oxide added PtAu nanoparticles-modified hybrid electrode

PubMed Central

Hossain, Md Faruk; Park, Jae Y.

2017-01-01

A highly sensitive amperometric glucose sensor was developed by immobilization of glucose oxidase (GOx) onto multi-layer reduced graphene oxide (MRGO) sheets decorated with platinum and gold flower-like nanoparticles (PtAuNPs) modified Au substrate electrode. The fabricated MRGO/PtAuNPs modified hybrid electrode demonstrated high electrocatalytic activities toward oxidation of H2O2, to which it had a wide linear response that ranged from 0.5 to 8 mM (R2 = 0.997), and high sensitivity of 506.25 μA/mMcm2. Furthermore, glucose oxidase-chitosan composite and cationic polydiallyldimethylammonium chloride (PDDA) were assembled by a casting method on the surface of MRGO/PtAuNPs modified electrode. This as-fabricated hybrid biosensor electrode exhibited high electrocatalytic activity for the detection of glucose in PBS. It demonstrated good analytical properties in terms of a low detection limit of 1 μM (signal-to-noise ratio of 3), short response time (3 s), high sensitivity (17.85 μA/mMcm2), and a wide linear range (0.01–8 mM) for glucose sensing. These results reveal that the newly developed sensing electrode offers great promise for new type enzymatic biosensor applications. PMID:28333943

Prenatal synthetic glucocorticoid treatment changes DNA methylation states in male organ systems: multigenerational effects.

PubMed

Crudo, Ariann; Petropoulos, Sophie; Moisiadis, Vasilis G; Iqbal, Majid; Kostaki, Alisa; Machnes, Ziv; Szyf, Moshe; Matthews, Stephen G

2012-07-01

Prenatal synthetic glucocorticoids (sGC) are administered to pregnant women at risk of delivering preterm, approximately 10% of all pregnancies. Animal studies have demonstrated that offspring exposed to elevated glucocorticoids, either by administration of sGC or as a result of maternal stress, are at increased risk of developing behavioral, endocrine, and metabolic abnormalities. DNA methylation is a covalent modification of DNA that plays a critical role in long-lasting programming of gene expression. Here we tested the hypothesis that prenatal sGC treatment has both acute and long-term effects on DNA methylation states in the fetus and offspring and that these effects extend into a subsequent generation. Pregnant guinea pigs were treated with sGC in late gestation, and methylation analysis by luminometric methylation assay was undertaken in organs from fetuses and offspring across two generations. Expression of genes that modify the epigenetic state were measured by quantitative real-time PCR. Results indicate that there are organ-specific developmental trajectories of methylation in the fetus and newborn. Furthermore, these trajectories are substantially modified by intrauterine exposure to sGC. These sGC-induced changes in DNA methylation remain into adulthood and are evident in the next generation. Furthermore, prenatal sGC exposure alters the expression of several genes encoding proteins that modulate the epigenetic state. Several of these changes are long lasting and are also present in the next generation. These data support the hypothesis that prenatal sGC exposure leads to broad changes in critical components of the epigenetic machinery and that these effects can pass to the next generation.

Atomically-thin molecular layers for electrode modification of organic transistors

NASA Astrophysics Data System (ADS)

Gim, Yuseong; Kang, Boseok; Kim, Bongsoo; Kim, Sun-Guk; Lee, Joong-Hee; Cho, Kilwon; Ku, Bon-Cheol; Cho, Jeong Ho

2015-08-01

Atomically-thin molecular layers of aryl-functionalized graphene oxides (GOs) were used to modify the surface characteristics of source-drain electrodes to improve the performances of organic field-effect transistor (OFET) devices. The GOs were functionalized with various aryl diazonium salts, including 4-nitroaniline, 4-fluoroaniline, or 4-methoxyaniline, to produce several types of GOs with different surface functional groups (NO2-Ph-GO, F-Ph-GO, or CH3O-Ph-GO, respectively). The deposition of aryl-functionalized GOs or their reduced derivatives onto metal electrode surfaces dramatically enhanced the electrical performances of both p-type and n-type OFETs relative to the performances of OFETs prepared without the GO modification layer. Among the functionalized rGOs, CH3O-Ph-rGO yielded the highest hole mobility of 0.55 cm2 V-1 s-1 and electron mobility of 0.17 cm2 V-1 s-1 in p-type and n-type FETs, respectively. Two governing factors: (1) the work function of the modified electrodes and (2) the crystalline microstructures of the benchmark semiconductors grown on the modified electrode surface were systematically investigated to reveal the origin of the performance improvements. Our simple, inexpensive, and scalable electrode modification technique provides a significant step toward optimizing the device performance by engineering the semiconductor-electrode interfaces in OFETs.Atomically-thin molecular layers of aryl-functionalized graphene oxides (GOs) were used to modify the surface characteristics of source-drain electrodes to improve the performances of organic field-effect transistor (OFET) devices. The GOs were functionalized with various aryl diazonium salts, including 4-nitroaniline, 4-fluoroaniline, or 4-methoxyaniline, to produce several types of GOs with different surface functional groups (NO2-Ph-GO, F-Ph-GO, or CH3O-Ph-GO, respectively). The deposition of aryl-functionalized GOs or their reduced derivatives onto metal electrode surfaces dramatically enhanced the electrical performances of both p-type and n-type OFETs relative to the performances of OFETs prepared without the GO modification layer. Among the functionalized rGOs, CH3O-Ph-rGO yielded the highest hole mobility of 0.55 cm2 V-1 s-1 and electron mobility of 0.17 cm2 V-1 s-1 in p-type and n-type FETs, respectively. Two governing factors: (1) the work function of the modified electrodes and (2) the crystalline microstructures of the benchmark semiconductors grown on the modified electrode surface were systematically investigated to reveal the origin of the performance improvements. Our simple, inexpensive, and scalable electrode modification technique provides a significant step toward optimizing the device performance by engineering the semiconductor-electrode interfaces in OFETs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03307a

Electrocatalytic performances of g-C3N4-LaNiO3 composite as bi-functional catalysts for lithium-oxygen batteries

PubMed Central

Wu, Yixin; Wang, Taohuan; Zhang, Yidie; Xin, Sen; He, Xiaojun; Zhang, Dawei; Shui, Jianglan

2016-01-01

A low cost and non-precious metal composite material g-C3N4-LaNiO3 (CNL) was synthesized as a bifunctional electrocatalyst for the air electrode of lithium-oxygen (Li-O2) batteries. The composition strategy changed the electron structure of LaNiO3 and g-C3N4, ensures high Ni3+/Ni2+ ratio and more absorbed hydroxyl on the surface of CNL that can promote the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The composite catalyst presents higher activities than the individual components g-C3N4 and LaNiO3 for both ORR and OER. In non-aqueous Li-O2 batteries, CNL shows higher capacity, lower overpotentials and better cycling stability than XC-72 carbon and LaNiO3 catalysts. Our results suggest that CNL composite is a promising cathode catalyst for Li-O2 batteries. PMID:27074882

Sensitive electrochemical detection of dopamine with a DNA/graphene bi-layer modified carbon ionic liquid electrode.

PubMed

Wang, Xiaofeng; You, Zheng; Sha, Hailiang; Cheng, Yong; Zhu, Huanhuan; Sun, Wei

2014-10-01

A DNA and graphene (GR) bi-layer modified carbon ionic liquid electrode (CILE) was fabricated by an electrodeposition method. GR nanosheets were electrodeposited on the surface of CILE at the potential of -1.3 V and then DNA was further deposited at the potential of +0.5 V on GR modified CILE. Electrochemical performances of the fabricated DNA/GR/CILE were carefully investigated. Then electrochemical behaviors of dopamine (DA) on the modified electrode were studied with the calculated electrochemical parameters. Under the optimized conditions, a linear relationship between the oxidation peak current and the concentration of DA was obtained in the range from 0.1 μmol/L to 1.0 mmol/L with a detection limit of 0.027 μmol/L (3σ). The modified electrode exhibited excellent reproducibility, repeatability, stability, validation and robustness for the electrochemical detection of DA. The proposed method was further applied to the DA injection solution and human urine samples determination with satisfactory results. Copyright © 2014 Elsevier B.V. All rights reserved.

Poly(amidosulfonic acid) modified glassy carbon electrode for determination of isoniazid in pharmaceuticals.

PubMed

Yang, Gongjun; Wang, Cunxiao; Zhang, Rui; Wang, Chenying; Qu, Qishu; Hu, Xiaoya

2008-06-01

Amidosulfonic acid was electropolymerized by cyclic voltammetry onto the surface of glassy carbon electrode (GCE) to fabricate the chemically modified electrode, which showed high stability, good selectivity and reproducibility for determination of isoniazid. The modified electrode showed an excellent electrocatalytical effect on the oxidation of isoniazid. Under the optimum conditions, there was a good linear relationship between anodic peak current and isoniazid concentration in the range of 5.0 x 10(-8)- 1.0 x 10(-5) M, and a detection limit of 1.0 x 10(-8) M (S/N = 3) was obtained after 120 s at the accumulation potential of - 0.2 V (vs. SCE). This developed method had been applied to the direct determination of isoniazid in injection and tablet samples with satisfactory results.

Synthesis of netlike gold nanoparticles using ampicillin as a stabilizing reagent and its application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Y.Z., E-mail: singyuanzhi@sina.com; Zhou, J.F.; Song, Y., E-mail: songyang@mail.buct.edu.cn

Graphical abstract: Electrochemical deposition of netlike gold nanoparticles (GNPs) on the surface of glassy carbon electrode and preparation of netlike GNPs in aqueous solution using ampicillin as a stabilizing reagent were proposed. The catalytic properties of netlike gold nanoparticles on the glassy carbon electrode for dopamine were demonstrated. The results indicate that the netlike gold nanoparticle modified electrode has an excellent repeatability and reproducibility. Display Omitted Highlights: ► Synthesis of netlike gold nanoparticles using ampicillin as a stabilizing reagent. ► Excellent repeatability and reproducibility of netlike gold nanoparticle modified glassy carbon electrode. ► The catalytic properties of netlike gold nanoparticlemore » for dopamine. -- Abstract: Electrochemical deposition of netlike gold nanoparticles on the surface of glassy carbon electrode and preparation of netlike GNPs in aqueous solution using ampicillin as a stabilizing reagent were proposed. The netlike gold nanoparticles were characterized by scanning electron microscope, transmission electron microscope, infrared spectrometer, UV spectrophotometer, powder X-ray diffractometer and electrochemical analyzer. The catalysis of the netlike gold nanoparticles on the glassy carbon electrode for dopamine was demonstrated. The results indicate that the gold nanoparticle modified electrode has an excellent repeatability and reproducibility.« less

Molecularly imprinted polymer based electrochemical detection of L-cysteine at carbon paste electrode.

PubMed

Aswini, K K; Vinu Mohan, A M; Biju, V M

2014-04-01

A methacrylic acid (MAA) based molecularly imprinted polymer (MIP) modified carbon paste electrode (CPE) was developed for electrochemical detection of L-cysteine (Cys). Characterisation of MIP was done with FTIR and the modified electrode with cyclic voltammetry (CV) and differential pulse voltammetry (DPV). CV, DPV and impedance analysis demonstrated that the modified electrode is responsive towards the target molecule. The optimum percentage composition of MIP for MIP/CPE and the effect of pH towards the electrode response for Cys were studied. The detection of Cys in the range of 2×10(-8) to 18×10(-8)M at MIP/CPE was monitored by DPV with a limit of detection of 9.6nM and R(2) of 0.9974. Also, various physiological interferents such as ascorbic acid, L-tryptophan, D-glucose, D-cysteine and L-cysteine were found to have little effect on DPV response at MIP/CPE. The utility of the electrode was proved by the effective detection of Cys from tap water and human blood plasma samples with reproducible results. Copyright © 2014 Elsevier B.V. All rights reserved.

The O2 reduction at the IFC modified O2 fuel cell electrode

NASA Technical Reports Server (NTRS)

Fielder, William L.; Singer, Joseph; Baldwin, Richard S.; Johnson, Richard E.

1992-01-01

The International Fuel Corporation (IFC) state of the art (SOA) O2 electrode (Au-10 percent Pt electrocatalyst by weight) is currently being used in the alkaline H2-O2 fuel cell in the NASA Space Shuttle. Recently, IFC modified O2 electrode, as a possible replacement for the SOA electrode. In the present study, O2 reduction data were obtained for the modified electrode at temperatures between 23.3 and 91.7 C. BET measurements gave an electrode BET surface area of about 2070 sq. cm/sq. cm of geometric surface area. The Tafel data could be fitted to two straight line regions. The slope for the lower region, designated as the 0.04 V/decade region, was temperature dependent, and the transfer coefficient was about 1.5. The 'apparent' energy of activation for this region was about 19 kcal/mol. An O2 reduction mechanism for this 0.04 region is presented. In the upper region, designated as the 0.08 V/decade region, diffusion may be the controlling process. Tafel data are presented to illustrate the increase in performance with increasing temperature.

Improving Single-Carbon-Nanotube-Electrode Contacts Using Molecular Electronics.

PubMed

Krittayavathananon, Atiweena; Ngamchuea, Kamonwad; Li, Xiuting; Batchelor-McAuley, Christopher; Kätelhön, Enno; Chaisiwamongkhol, Korbua; Sawangphruk, Montree; Compton, Richard G

2017-08-17

We report the use of an electroactive species, acetaminophen, to modify the electrical connection between a carbon nanotube (CNT) and an electrode. By applying a potential across two electrodes, some of the CNTs in solution occasionally contact the electrified interface and bridge between two electrodes. By observing a single CNT contact between two microbands of an interdigitated Au electrode in the presence and absence of acetaminophen, the role of the molecular species at the electronic junction is revealed. As compared with the pure CNT, the current magnitude of the acetaminophen-modified CNTs significantly increases with the applied potentials, indicating that the molecule species improves the junction properties probably via redox shuttling.

Graphene-bimetallic nanoparticle composites with enhanced electro-catalytic detection of bisphenol A

NASA Astrophysics Data System (ADS)

Pogacean, Florina; Biris, Alexandru R.; Socaci, Crina; Coros, Maria; Magerusan, Lidia; Rosu, Marcela-Corina; Lazar, Mihaela D.; Borodi, Gheorghe; Pruneanu, Stela

2016-12-01

This study brings for the first time novel knowledge about the synthesis by catalytic chemical vapor deposition with induction heating of graphene-bimetallic nanoparticle composites (Gr-AuCu and Gr-AgCu) and their morphological and structural characterization by transmission electron microscopy, Raman spectroscopy, and x-ray powder diffraction. Gold electrodes modified with the obtained materials exhibit an enhanced electro-catalytic effect towards one of the most encountered estrogenic disruptive chemicals, bisphenol A (BPA). The BPA behavior in varying pH solutions was investigated using the electrochemical quartz crystal microbalance, which allowed the accurate determination of the number of molecules involved in the oxidation process. The modified electrodes promote the oxidation of BPA at significantly lower potentials (0.66 V) compared to bare gold (0.78 V). In addition, the peak current density recorded with such electrodes greatly exceeded that obtained with bare gold (e.g. one order of magnitude larger, for a Au/Gr-AgCu electrode). The two modified electrodes have low detection limits, of 1.31 × 10-6 M and 1.91 × 10-6 M for Au/Gr-AgCu and Au/Gr-AuCu, respectively. The bare gold electrode has a higher detection limit of 5.1 × 10-6 M. The effect of interfering species (e.g. catechol and 3-nitrophenol) was also investigated. Their presence influenced not only the BPA peak potential, but also the peak current. With both modified electrodes, no peak currents were recorded below 3 × 10-5 M BPA.

Silver Nanoparticle Modified Electrode Covered by Graphene Oxide for the Enhanced Electrochemical Detection of Dopamine

PubMed Central

Shin, Jae-Wook; Kim, Kyeong-Jun; Yoon, Jinho; Jo, Jinhee; El-Said, Waleed Ahmed; Choi, Jeong-Woo

2017-01-01

Several neurological disorders such as Alzheimer’s disease and Parkinson’s disease have become a serious impediment to aging people nowadays. One of the efficient methods used to monitor these neurological disorders is the detection of neurotransmitters such as dopamine. Metal materials, such as gold and platinum, are widely used in this electrochemical detection method; however, low sensitivity and linearity at low dopamine concentrations limit the use of these materials. To overcome these limitations, a silver nanoparticle (SNP) modified electrode covered by graphene oxide for the detection of dopamine was newly developed in this study. For the first time, the surface of an indium tin oxide (ITO) electrode was modified using SNPs and graphene oxide sequentially through the electrochemical deposition method. The developed biosensor provided electrochemical signal enhancement at low dopamine concentrations in comparison with previous biosensors. Therefore, our newly developed SNP modified electrode covered by graphene oxide can be used to monitor neurological diseases through electrochemical signal enhancement at low dopamine concentrations. PMID:29186040

Silver Nanoparticle Modified Electrode Covered by Graphene Oxide for the Enhanced Electrochemical Detection of Dopamine.

PubMed

Shin, Jae-Wook; Kim, Kyeong-Jun; Yoon, Jinho; Jo, Jinhee; El-Said, Waleed Ahmed; Choi, Jeong-Woo

2017-11-29

Several neurological disorders such as Alzheimer's disease and Parkinson's disease have become a serious impediment to aging people nowadays. One of the efficient methods used to monitor these neurological disorders is the detection of neurotransmitters such as dopamine. Metal materials, such as gold and platinum, are widely used in this electrochemical detection method; however, low sensitivity and linearity at low dopamine concentrations limit the use of these materials. To overcome these limitations, a silver nanoparticle (SNP) modified electrode covered by graphene oxide for the detection of dopamine was newly developed in this study. For the first time, the surface of an indium tin oxide (ITO) electrode was modified using SNPs and graphene oxide sequentially through the electrochemical deposition method. The developed biosensor provided electrochemical signal enhancement at low dopamine concentrations in comparison with previous biosensors. Therefore, our newly developed SNP modified electrode covered by graphene oxide can be used to monitor neurological diseases through electrochemical signal enhancement at low dopamine concentrations.

Preparation of chitosan grafted graphite composite for sensitive detection of dopamine in biological samples.

PubMed

Palanisamy, Selvakumar; Thangavelu, Kokulnathan; Chen, Shen-Ming; Gnanaprakasam, P; Velusamy, Vijayalakshmi; Liu, Xiao-Heng

2016-10-20

The accurate detection of dopamine (DA) levels in biological samples such as human serum and urine are essential indicators in medical diagnostics. In this work, we describe the preparation of chitosan (CS) biopolymer grafted graphite (GR) composite for the sensitive and lower potential detection of DA in its sub micromolar levels. The composite modified electrode has been used for the detection of DA in biological samples such as human serum and urine. The GR-CS composite modified electrode shows an enhanced oxidation peak current response and low oxidation potential for the detection of DA than that of electrodes modified with bare, GR and CS discretely. Under optimum conditions, the fabricated GR-CS composite modified electrode shows the DPV response of DA in the linear response ranging from 0.03 to 20.06μM. The detection limit and sensitivity of the sensor were estimated as 0.0045μM and 6.06μA μM(-1)cm(-2), respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biosensing applications of titanium dioxide coated graphene modified disposable electrodes.

PubMed

Kuralay, Filiz; Tunç, Selma; Bozduman, Ferhat; Oksuz, Lutfi; Oksuz, Aysegul Uygun

2016-11-01

In the present work, preparation of titanium dioxide coated graphene (TiO2/graphene) and the use of this nanocomposite modified electrode for electrochemical biosensing applications were detailed. The nanocomposite was prepared with radio frequency (rf) rotating plasma method which serves homogeneous distribution of TiO2 onto graphene. TiO2/graphene was characterized with scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) analysis. Then, this nanocomposite was dissolved in phosphate buffer solution (pH 7.4) and modified onto disposable pencil graphite electrode (PGE) by dip coating for the investigation of the biosensing properties of the prepared electrode. TiO2/graphene modified PGE was characterized with SEM, EDS and cyclic voltammetry (CV). The sensor properties of the obtained surface were examined for DNA and DNA-drug interaction. The detection limit was calculated as 1.25mgL(-1) (n=3) for double-stranded DNA (dsDNA). RSD% was calculated as 2.4% for three successive determinations at 5mgL(-1) dsDNA concentration. Enhanced results were obtained compared to the ones obtained with graphene and unmodified (bare) electrodes. Copyright © 2016 Elsevier B.V. All rights reserved.

Electrochemical sensor for ranitidine determination based on carbon paste electrode modified with oxovanadium (IV) salen complex.

PubMed

Raymundo-Pereira, Paulo A; Teixeira, Marcos F S; Fatibello-Filho, Orlando; Dockal, Edward R; Bonifácio, Viviane Gomes; Marcolino, Luiz H

2013-10-01

The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicyllideneiminato)oxovanadium (IV) complex ([VO(salen)]) as well as its application for ranitidine determination are described. The electrochemical behavior of the modified electrode for the electroreduction of ranitidine was investigated using cyclic voltammetry, and analytical curves were obtained for ranitidine using linear sweep voltammetry (LSV) under optimized conditions. The best voltammetric response was obtained for an electrode composition of 20% (m/m) [VO(salen)] in the paste, 0.10 mol L(-1) of KCl solution (pH 5.5 adjusted with HCl) as supporting electrolyte and scan rate of 25 mV s(-1). A sensitive linear voltammetric response for ranitidine was obtained in the concentration range from 9.9×10(-5) to 1.0×10(-3) mol L(-1), with a detection limit of 6.6×10(-5) mol L(-1) using linear sweep voltammetry. These results demonstrated the viability of this modified electrode as a sensor for determination, quality control and routine analysis of ranitidine in pharmaceutical formulations. Copyright © 2013. Published by Elsevier B.V.

Bromination of Aromatic Compounds by Residual Bromide in Sodium Chloride Matrix Modifier Salt During Heated Headspace GC/MS Analysis

EPA Science Inventory

Analytical artifacts attributed to the bromination of toluene, xylenes, and trimethylbenzenes were found during the heated headspace gas chromatography/mass spectrometry (GC/MS) analysis of aqueous samples. The aqueous samples were produced from Fenton-like chemical oxidation rea...

Preparation of boron doped diamond modified by iridium for electroreduction of carbon dioxide (CO2)

NASA Astrophysics Data System (ADS)

Ichzan, A. M.; Gunlazuardi, J.; Ivandini, T. A.

2017-04-01

Electroreduction of carbon dioxide (CO2) at iridium oxide-modified boron-doped diamond (IrOx-BDD) electrodes in aqueous electrolytes was studied by voltammetric method. The aim of this study was to find out the catalytic effect of IrOx to produce fine chemicals contained of two or more carbon atoms (for example acetic acid) in high percentage. Characterization using FE-SEM and XPS indicated that IrO2 can be deposited at BDD electrode, whereas characterization using cyclic voltammetry indicated that the electrode was applicable to be used as working electrode for CO2 electroreduction.

Cloud Point Extraction for Electroanalysis: Anodic Stripping Voltammetry of Cadmium.

PubMed

Rusinek, Cory A; Bange, Adam; Papautsky, Ian; Heineman, William R

2015-06-16

Cloud point extraction (CPE) is a well-established technique for the preconcentration of hydrophobic species from water without the use of organic solvents. Subsequent analysis is then typically performed via atomic absorption spectroscopy (AAS), UV-vis spectroscopy, or high performance liquid chromatography (HPLC). However, the suitability of CPE for electroanalytical methods such as stripping voltammetry has not been reported. We demonstrate the use of CPE for electroanalysis using the determination of cadmium (Cd(2+)) by anodic stripping voltammetry (ASV). Rather than using the chelating agents which are commonly used in CPE to form a hydrophobic, extractable metal complex, we used iodide and sulfuric acid to neutralize the charge on Cd(2+) to form an extractable ion pair. This offers good selectivity for Cd(2+) as no interferences were observed from other heavy metal ions. Triton X-114 was chosen as the surfactant for the extraction because its cloud point temperature is near room temperature (22-25 °C). Bare glassy carbon (GC), bismuth-coated glassy carbon (Bi-GC), and mercury-coated glassy carbon (Hg-GC) electrodes were compared for the CPE-ASV. A detection limit for Cd(2+) of 1.7 nM (0.2 ppb) was obtained with the Hg-GC electrode. ASV with CPE gave a 20x decrease (4.0 ppb) in the detection limit compared to ASV without CPE. The suitability of this procedure for the analysis of tap and river water samples was demonstrated. This simple, versatile, environmentally friendly, and cost-effective extraction method is potentially applicable to a wide variety of transition metals and organic compounds that are amenable to detection by electroanalytical methods.

Label-Free Electrochemical Detection of Vanillin through Low-Defect Graphene Electrodes Modified with Au Nanoparticles.

PubMed

Gao, Jingyao; Yuan, Qilong; Ye, Chen; Guo, Pei; Du, Shiyu; Lai, Guosong; Yu, Aimin; Jiang, Nan; Fu, Li; Lin, Cheng-Te; Chee, Kuan W A

2018-03-25

Graphene is an excellent modifier for the surface modification of electrochemical electrodes due to its exceptional physical properties and, for the development of graphene-based chemical and biosensors, is usually coated on glassy carbon electrodes (GCEs) via drop casting. However, the ease of aggregation and high defect content of reduced graphene oxides degrade the electrical properties. Here, we fabricated low-defect graphene electrodes by catalytically thermal treatment of HPHT diamond substrate, followed by the electrodeposition of Au nanoparticles (AuNPs) with an average size of ≈60 nm on the electrode surface using cyclic voltammetry. The Au nanoparticle-decorated graphene electrodes show a wide linear response range to vanillin from 0.2 to 40 µM with a low limit of detection of 10 nM. This work demonstrates the potential applications of graphene-based hybrid electrodes for highly sensitive chemical detection.

Electrochemical analysis of gold-coated magnetic nanoparticles for detecting immunological interaction

NASA Astrophysics Data System (ADS)

Pham, Thao Thi-Hien; Sim, Sang Jun

2010-01-01

An electrochemical impedance immunosensor was developed for detecting the immunological interaction between human immunoglobulin (IgG) and protein A from Staphylococcus aureus based on the immobilization of human IgG on the surface of modified gold-coated magnetic nanoparticles. The nanoparticles with an Au shell and Fe oxide cores were functionalized by a self-assembled monolayer of 11-mercaptoundecanoic acid. The electrochemical analysis was conducted on the modified magnetic carbon paste electrodes with the nanoparticles. The magnetic nanoparticles were attached to the surface of the magnetic carbon paste electrodes via magnetic force. The cyclic voltammetry technique and electrochemical impedance spectroscopy measurements of the magnetic carbon paste electrodes coated with magnetic nanoparticles-human IgG complex showed changes in its alternating current (AC) response both after the modification of the surface of the electrode and the addition of protein A. The immunological interaction between human IgG on the surface of the modified magnetic carbon paste electrodes and protein A in the solution could be successfully monitored.

A non-enzymatic sensor for hydrogen peroxide based on polyaniline, multiwalled carbon nanotubes and gold nanoparticles modified Au electrode.

PubMed

Narang, Jagriti; Chauhan, Nidhi; Pundir, C S

2011-11-07

We describe the construction of a polyaniline (PANI), multiwalled carbon nanotubes (MWCNTs) and gold nanoparticles (AuNPs) modified Au electrode for determination of hydrogen peroxide without using peroxidase (HRP). The AuNPs/MWCNT/PANI composite film deposited on Au electrode was characterized by Scanning Electron Microscopy (SEM) and electrochemical methods. Cyclic voltammetric (CV) studies of the electrode at different stages of construction demonstrated that the modified electrode had enhanced electrochemical oxidation of H(2)O(2), which offers a number of attractive features to develop amperometric sensors based on split of H(2)O(2). The amperometric response to H(2)O(2) showed a linear relationship in the range from 3.0 μM to 600.0 μM with a detection limit of 0.3 μM (S/N = 3) and with high sensitivity of 3.3 mA μM(-1). The sensor gave accurate and satisfactory results, when employed for determination of H(2)O(2) in milk and urine.

Probing the electrochemical double layer of an ionic liquid using voltammetry and impedance spectroscopy: a comparative study of carbon nanotube and glassy carbon electrodes in [EMIM](+)[EtSO(4)](-).

PubMed

Zheng, J P; Goonetilleke, P C; Pettit, C M; Roy, D

2010-05-15

Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are compared as techniques for analyzing double layer capacitances of ionic liquids (ILs) at the surfaces of two carbon-based electrodes. These systems are relevant for energy storage supercapacitors and often are associated with unconventional electrochemical properties. Certain theoretical and experimental aspects of CV and EIS necessary for quantitative evaluation of the capacitance characteristics of such systems are explored. The experiments use 1-ethyl-3-methyl imidazolium ethylsulfate as a model IL electrolyte in combination with a porous electrode of carbon nanotubes (CNTs). The results are compared with those obtained with a nonporous glassy carbon (GC) electrode. The time is constant, and hence the power delivery characteristics of the experimental cell are affected by the electrolyte resistance and residual faradaic reactions of the IL, as well as by the spatially inhomogeneous electrode surfaces. It is shown that adequate characterization of these IL-electrode systems can be achieved by combining CV with EIS. A phenomenological framework for utilizing this combination is discussed.

Supercapacitors based on modified graphene electrodes with poly(ionic liquid)

NASA Astrophysics Data System (ADS)

Trigueiro, João Paulo C.; Lavall, Rodrigo L.; Silva, Glaura G.

2014-06-01

The improved accessibility of the electrolyte to the surface of carbon nanomaterials is a challenge to be overcome in supercapacitors based on ionic liquid electrolytes. In this study, we report the preparation of supercapacitors based on reduced graphene oxide (RGO) electrodes and ionic liquid as the electrolyte (specifically, 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide or [MPPy][TFSI]). Two types of electrodes were compared: the RGO-based electrode and a poly(ionic liquid)-modified RGO electrode (PIL:RGO). The supercapacitor produced with the PIL:RGO electrode and [MPPy][TFSI] showed an electrochemical stability of 3 V and provided a capacitance of 71.5 F g-1 at room temperature; this capacitance is 130% higher with respect to the RGO-based supercapacitor. The decrease of the specific capacitance after 2000 cycles is only 10% for the PIL:RGO-based device. The results revealed the potential of the PIL:RGO material as an electrode for supercapacitors. This composite electrode increases the compatibility with the ionic liquid electrolyte compared to an RGO electrode, promoting an increase in the effective surface area of the electrode accessible to the electrolyte ions.

Polyoxometalate-Graphene Nanocomposite Modified Electrode for Electrocatalytic Detection of Ascorbic Acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Weiying; Du, Dan; Gunaratne, Don

Phosphomolybdate functionalized graphene nanocomposite (PMo 12-GS) has been successfully formed on a glassy carbon electrode (GCE) for the detection of ascorbic acid (AA). The obtained PMo 12-GS modified GCE, was characterized by cyclic voltammetry, electrochemical impedance spectroscopy, scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy and compared with GCE, GS modified GCE, and PMo 12 modified GCE. It shows an increased current and a decrease in over-potential of ~210 mV. The amperometric signals are linearly proportional to the AA concentration in a wide concentration range from 1×10 -6 M to 8×10 -3 M, with a detection limit ofmore » 0.5×10 -6 M. Finally, the PMo 12-GS modified electrode was employed for the determination of the AA level in vitamin C tablets, with recoveries between 96.3 and 100.8 %.« less

Covalently coupled hybrid of graphitic carbon nitride with reduced graphene oxide as a superior performance lithium-ion battery anode

NASA Astrophysics Data System (ADS)

Fu, Yongsheng; Zhu, Junwu; Hu, Chong; Wu, Xiaodong; Wang, Xin

2014-10-01

An in situ chemical synthetic approach has been designed for the fabrication of a covalently coupled hybrid consisting of graphitic carbon nitride (g-C3N4) with reduced graphene oxide (rGO) with differing g-C3N4/rGO ratio. The epoxy groups of graphene oxide (GO) undergo a nucleophilic substitution reaction with dicyandiamide (C2H4N4) to form the C2H4N4-GO composite via a covalent C-N bond, and then both the in situ polymerization of C2H4N4 and the thermal reduction of GO can be achieved at higher temperatures, forming the covalently coupled g-C3N4-rGO. FT-IR, CP-MAS NMR and XPS analyses, clearly revealed a covalent interaction between the g-C3N4 and rGO sheets. The g-C3N4-rGO exhibits an unprecedented high, stable and reversible capacity of 1525 mA h g-1 at a current density of 100 mA g-1 after 50 cycles. Even at a large current density of 1000 mA g-1, a reversible capacity of 943 mA h g-1 can still be retained. The superior electrochemical performance of g-C3N4-rGO is attributed to the specific characteristics of the unique nanostructure of g-C3N4-rGO and the concerted effects of g-C3N4 and rGO, including covalent interactions between the two moieties, the good conductivity and high special surface area of the nanocomposite, as well as the template effect of the planar amino group of g-C3N4 for the dispersed decoration of Li+ ions.An in situ chemical synthetic approach has been designed for the fabrication of a covalently coupled hybrid consisting of graphitic carbon nitride (g-C3N4) with reduced graphene oxide (rGO) with differing g-C3N4/rGO ratio. The epoxy groups of graphene oxide (GO) undergo a nucleophilic substitution reaction with dicyandiamide (C2H4N4) to form the C2H4N4-GO composite via a covalent C-N bond, and then both the in situ polymerization of C2H4N4 and the thermal reduction of GO can be achieved at higher temperatures, forming the covalently coupled g-C3N4-rGO. FT-IR, CP-MAS NMR and XPS analyses, clearly revealed a covalent interaction between the g-C3N4 and rGO sheets. The g-C3N4-rGO exhibits an unprecedented high, stable and reversible capacity of 1525 mA h g-1 at a current density of 100 mA g-1 after 50 cycles. Even at a large current density of 1000 mA g-1, a reversible capacity of 943 mA h g-1 can still be retained. The superior electrochemical performance of g-C3N4-rGO is attributed to the specific characteristics of the unique nanostructure of g-C3N4-rGO and the concerted effects of g-C3N4 and rGO, including covalent interactions between the two moieties, the good conductivity and high special surface area of the nanocomposite, as well as the template effect of the planar amino group of g-C3N4 for the dispersed decoration of Li+ ions. Electronic supplementary information (ESI) available: N species content (at%) of g-C3N4-rGO-1 based on XPS analysis; the first cycle discharge capacity, charge capacity and coulombic efficiency for the g-C3N4, rGO, and g-C3N4-rGO-n (n = 0.25, 0.5, 1, 2, 3) electrodes; nitrogen adsorption/desorption isotherm of g-C3N4; cycle performance of the g-C3N4-rGO-n (n = 0.25, 0.5, 3) electrodes at a current rate of 100 mA g-1 between 3.0 and 0.01 V versus Li+/Li. See DOI: 10.1039/c4nr03145h

Detection of Guanine and Adenine Using an Aminated Reduced Graphene Oxide Functional Membrane-Modified Glassy Carbon Electrode

PubMed Central

Li, Di; Yang, Xiao-Lu; Xiao, Bao-Lin; Geng, Fang-Yong; Hong, Jun; Sheibani, Nader; Moosavi-Movahedi, Ali Akbar

2017-01-01

A new electrochemical sensor based on a Nafion, aminated reduced graphene oxide and chitosan functional membrane-modified glassy carbon electrode was proposed for the simultaneous detection of adenine and guanine. Fourier transform-infrared spectrometry (FTIR), transmission electron microscopy (TEM), and electrochemical methods were utilized for the additional characterization of the membrane materials. The prepared electrode was utilized for the detection of guanine (G) and adenine (A). The anodic peak currents to G and A were linear in the concentrations ranging from 0.1 to 120 μM and 0.2 to 110 μM, respectively. The detection limits were found to be 0.1 μM and 0.2 μM, respectively. Moreover, the modified electrode could also be used to determine G and A in calf thymus DNA. PMID:28718793

Simultaneous quantification of arginine, alanine, methionine and cysteine amino acids in supplements using a novel bioelectro-nanosensor based on CdSe quantum dot/modified carbon nanotube hollow fiber pencil graphite electrode via Taguchi method.

PubMed

Hooshmand, Sara; Es'haghi, Zarrin

2017-11-30

A number of four amino acids have been simultaneously determined at CdSe quantum dot-modified/multi-walled carbon nanotube hollow fiber pencil graphite electrode in different bodybuilding supplements. CdSe quantum dots were synthesized and applied to construct a modified carbon nanotube hollow fiber pencil graphite electrode. FT-IR, TEM, XRD and EDAX methods were applied for characterization of the synthesized CdSe QDs. The electro-oxidation of arginine (Arg), alanine (Ala), methionine (Met) and cysteine (Cys) at the surface of the modified electrode was studied. Then the Taguchi's method was applied using MINITAB 17 software to find out the optimum conditions for the amino acids determination. Under the optimized conditions, the differential pulse (DP) voltammetric peak currents of Arg, Ala, Met and Cys increased linearly with their concentrations in the ranges of 0.287-33670μM and detection limits of 0.081, 0.158, 0.094 and 0.116μM were obtained for them, respectively. Satisfactory results were achieved for calibration and validation sets. The prepared modified electrode represents a very good resolution between the voltammetric peaks of the four amino acids which makes it suitable for the detection of each in presence of others in real samples. Copyright © 2017. Published by Elsevier B.V.

A novel l-leucine modified Sol-Gel-Carbon electrode for simultaneous electrochemical detection of homovanillic acid, dopamine and uric acid in neuroblastoma diagnosis.

PubMed

Khamlichi, Redouan El; Bouchta, Dounia; Anouar, El Hassane; Atia, Mounia Ben; Attar, Aisha; Choukairi, Mohamed; Tazi, Saloua; Ihssane, Raissouni; Faiza, Chaoukat; Khalid, Draoui; Khalid, Riffi Temsamani

2017-02-01

Neuroblastoma is a pediatric neuroblastic tumor arising in the sympathetic nervous crest cells. A high grade of Neuroblastoma is characterized by a high urinary excretion of homovanillic acid and dopamine. In this work l-leucine modified Sol-Gel-Carbon electrode was used for a sensitive voltammetric determination of homovanillic acid and dopamine in urine. The electrochemical response characteristics were investigated by cyclic and differential pulse voltammetry; the modified electrode has shown an increase in the effective area of up to 40%, a well-separated oxidation peaks and an excellent electrocatalytic activity. High sensitivity and selectivity in the linear range of 0,4-100μML -1 of homovanillic acid and 10-120μML -1 of dopamine were also obtained. Moreover, a sub-micromolar limit of detection of 0.1μM for homovanillic acid and 1.0μM for the dopamine was achieved. Indeed, high reproducibility with simple preparation and regeneration of the electrode surface made this electrode very suitable for the determination of homovanillic acid and dopamine in pharmaceutical and clinical preparations. The mechanism of homovanillic acid and the electrochemical oxidation at l-leucine modified Sol-Gel-Carbon electrode is described out the B3P86/6-31+G(d,p) level of theory as implemented in Gaussian software. Copyright © 2016 Elsevier B.V. All rights reserved.

An amperometric bienzymatic cholesterol biosensor based on functionalized graphene modified electrode and its electrocatalytic activity towards total cholesterol determination.

PubMed

Manjunatha, Revanasiddappa; Shivappa Suresh, Gurukar; Melo, Jose Savio; D'Souza, Stanislaus F; Venkatesha, Thimmappa Venkatarangaiah

2012-09-15

Cholesterol oxidase (ChOx) and cholesterol esterase (ChEt) have been covalently immobilized onto functionalized graphene (FG) modified graphite electrode. Enzymes modified electrodes were characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). FG accelerates the electron transfer from electrode surface to the immobilized ChOx, achieving the direct electrochemistry of ChOx. A well defined redox peak was observed, corresponding to the direct electron transfer of the FAD/FADH(2) of ChOx. The electron transfer coefficient (α) and electron transfer rate constant (K(s)) were calculated and their values are found to be 0.31 and 0.78 s(-1), respectively. For the free cholesterol determination, ChOx-FG/Gr electrode exhibits a sensitive response from 50 to 350 μM (R=-0.9972) with a detection limit of 5 μM. For total cholesterol determination, co-immobilization of ChEt and ChOx on modified electrode, i.e. (ChEt/ChOx)-FG/Gr electrode showed linear range from 50 to 300 μM (R=-0.9982) with a detection limit of 15 μM. Some common interferents like glucose, ascorbic acid and uric acid did not cause any interference, due to the use of a low operating potential. The FG/Gr electrode exhibits good electrocatalytic activity towards hydrogen peroxide (H(2)O(2)). A wide linear response to H(2)O(2) ranging from 0.5 to 7 mM (R=-0.9967) with a sensitivity of 443.25 μA mM(-1) cm(-2) has been obtained. Copyright © 2012 Elsevier B.V. All rights reserved.

Study on the Pulsed Flashover Characteristics of Solid-Solid Interface in Electrical Devices Poured by Epoxy Resin

NASA Astrophysics Data System (ADS)

Li, Manping; Wu, Kai; Yang, Zhanping; Ding, Man; Liu, Xin; Cheng, Yonghong

2014-09-01

In electrical devices poured by epoxy resin, there are a lot of interfaces between epoxy resin and other solid dielectrics, i.e. solid-solid interfaces. Experiments were carried out to study the flashover characteristics of two typical solid-solid interfaces (epoxy-ceramic and epoxy-PMMA) under steep high-voltage impulse for different electrode systems (coaxial electrodes and finger electrodes) and different types of epoxy resin (neat epoxy resin, polyether modified epoxy resin and polyurethane modified epoxy resin). Results showed that, the flashover of solid-solid interface is similar to the breakdown of solid dielectric, and there are unrecoverable carbonated tracks after flashover. Under the same distance of electrodes, the electric stress of coaxial electrodes is lower than that of finger electrodes; and after the flashover, there are more severe breakdown and larger enhanced surface conductivity at interface for coaxial electrodes, as compared with the case of finger electrode. The dielectric properties are also discussed.

Evaluation of Thermal Oxidative Aging Effect on the Rheological Performance of Modified Asphalt Binders

NASA Astrophysics Data System (ADS)

Zhu, Cheng

Modified asphalt binder, which is combined by base binder and additive modifier, has been implemented in pavement industry for more than 30 years. Recently, the oxidative aging mechanism of asphalt binder has been studied for several decades, and appreciable finding results of asphalt binder aging mechanism were achieved from the chemistry and rheological performance aspects. However, most of these studies were conducted with neat binders, the research of aging mechanism of modified asphalt binder was limited. Nowadays, it is still highly necessary to clarify how the asphalt binder aging happens with the modified asphalt binder, what is the effect of the different modifiers (additives) on the binder aging process, how the rheological performance changes under the thermal oxidative aging conditions and so on. The objective of this study was to investigate the effect of isothermal oxidative aging conditions on the rheological performance change of the modified and controlled asphalt binders. There were totally 14 different sorts of asphalt binders had been aged in the PAV pans in the air-force drafted ovens at 50°C, 60°C and 85°C for 0.5 day to 240 days. The Fourier-Transform Infrared Spectroscopy (FT-IR) and Dynamic Shear Rheometer (DSR) were used to perform the experiments. The analysis of rheological indices (Low shear viscosity-LSV, Crossover modulus-G*c, Glover-Rowe Parameter-G-R, DSR function-DSR Fn) as a function of carbonyl area (CA) was conducted. With the SBS modification, both of the hardening susceptibility of the rheological index-LSV and G-R decreases compared with the corresponding base binder. The TR increased the hardening susceptibility of all the rheological indexes. While for the G*c, SBS increases the slope of the most modified asphalt binders except A and B_TR_X series binders. The multiple linear regression statistical analysis results indicate that the oxidative aging conditions play an important role on the CA, and rheological performance indexes. The modifiers-SBS and TR have different directional effect on these parameters. The field asphalt binder carbonyl area prediction was conducted. The pavement temperatures which were calculated by TEMP software were input into MATLAB(TM) as a parameter with other factors, e.g the asphalt binder oxidative aging parameters, the binder film thickness, the air void radius, etc., to calculate the field asphalt CA value as a function of time out to 20 years. It was found that the different rheological index method resulted different conclusion with the asphalt binder. The SBS modified asphalt binders of A, C version and B version had close average increasing rate of LSV, higher average decreasing rate of G*c, lower average increasing rate of DSR Fn compared with the corresponding base binders. D_HPM had lower average increasing rate of LSV, G*c and DSR Fn than base binder Base D. The tire rubber modified binder B_TR had higher average increasing rate of LSV, DSR Fn, and higher average decreasing rate of G*c than base binder Base B. The main finding of this study was that the modifier SBS and tire rubber can reduce the thermal oxidation aging rate (kf and kc) compared with the corresponding base binder, the activation energy was asphalt binder source dependent. For the hardening susceptibility, the modifiers-SBS, X, Y, Z reduced the HS of LSV and G-R. The tire rubber slightly increased the HS of LSV and G-R. A_PM, B_TR_X_PM reduced the HS of G*c and other modified binders increased the HS of G*c.

Photoactive films of photosystem I on transparent reduced graphene oxide electrodes.

PubMed

Darby, Emily; LeBlanc, Gabriel; Gizzie, Evan A; Winter, Kevin M; Jennings, G Kane; Cliffel, David E

2014-07-29

Photosystem I (PSI) is a photoactive electron-transport protein found in plants that participates in the process of photosynthesis. Because of PSI's abundance in nature and its efficiency with charge transfer and separation, there is a great interest in applying the protein in photoactive electrodes. Here, we developed a completely organic, transparent, conductive electrode using reduced graphene oxide (RGO) on which a multilayer of PSI could be deposited. The resulting photoactive electrode demonstrated current densities comparable to that of a gold electrode modified with a multilayer film of PSI and significantly higher than that of a graphene electrode modified with a monolayer film of PSI. The relatively large photocurrents produced by integrating PSI with RGO and using an opaque, organic mediator can be applied to the facile production of more economic solar energy conversion devices.

Studies of Aqueous and Non-Aqueous Electrochemical Interface for Applications in Microelectronic and Energy Storage Systems

NASA Astrophysics Data System (ADS)

Zheng, Jianping

Various electrochemical techniques were utilized to study a wide range of electrochemical systems in this dissertation. Mainly they are grouped in three sections: 1) the conventional metal-aqueous systems for new applications in modern microelectronic devices, 2) unconventional ceramic-organic systems for applications in Li-ion batteries and 3) novel systems composed of ionic liquids and carbon series electrodes. The objects are to probe the electrochemical/chemical reactions and interfacial structures, which are the common features of the aforementioned systems. This dissertation mainly focuses on experimental aspects, however, some theories and new models used to elucidate the experiment data have also been developed and presented. Some new experimental techniques have been explored and their limitations and validity have also been discussed. Oxalic acid (OA)-based nonalkaline solutions with H2O 2 are found to support chemically mediated removal of Ta-oxide surface films on Ta. The associated surface reactions are critical for chemical mechanical planarization (CMP) of Ta barrier. In chapter 4, a Ta coupon electrode is used as a model system in abrasive-free solutions of OA and H2O 2, where the chemical component of CMP is selectively examined. In chapter 5, electrochemical impedance spectroscopy (EIS) is employed to study the competitive reactions of surface corrosion and passivating film formation on a Cu-rotating disc electrode (RDE) in pH-adjusted solutions of H2O2, acetic acid (HAc) and ammonium dodecyl sulfate (ADS). Micrometric LiMn2O4 particles are mechano-chemically modified by ball-milling to obtain a mixture of nano- and micro-scale particles. In chapter 6, this mixture is tested as a potential active cathode material for rapid-charge Li ion batteries, and also as a model system for studying the detailed kinetics of Li intercalation/de-intercalation in such electrodes. In chapter 7, cyclic voltammetry (CV) and EIS are compared as techniques for analyzing double layer capacitances of ionic liquids (ILs) at the surfaces of two carbon-based electrodes. These systems are relevant for energy storage supercapacitors and often are associated with unconventional electrochemical properties. In chapter 8, the electrochemical interfaces of a glassy carbon (GC) and a carbon nanotube (CNT) paper electrode have been studied in EmimBF 4 and BmimBF4 ILs using CV and EIS.

Voltammetric behavior of dopamine at a glassy carbon electrode modified with NiFe(2)O(4) magnetic nanoparticles decorated with multiwall carbon nanotubes.

PubMed

Ensafi, Ali A; Arashpour, B; Rezaei, B; Allafchian, Ali R

2014-06-01

Voltammetric behavior of dopamine was studied on a glassy carbon electrode (GCE) modified-NiFe(2)O(4) magnetic nanoparticles decorated with multiwall carbon nanotubes. Impedance spectroscopy and cyclic voltammetry were used to characterize the behavior of dopamine at the surface of modified-GCE. The modified electrode showed a synergic effect toward the oxidation of dopamine. The oxidation peak current is increased linearly with the dopamine concentration (at pH7.0) in wide dynamic ranges of 0.05-6.0 and 6.0-100μmolL(-1) with a detection limit of 0.02μmolL(-1), using differential pulse voltammetry. The selectivity of the method was studied and the results showed that the modified electrode is free from interference of organic compounds especially ascorbic acid, uric acid, cysteine and urea. Its applicability in the determination of dopamine in pharmaceutical, urine samples and human blood serum was also evaluated. The proposed electrochemical sensor has appropriate properties such as high selectivity, low detection limit and wide linear dynamic range when compared with that of the previous reported papers for dopamine detection. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrochemically reduced graphene oxide/Poly-Glycine composite modified electrode for sensitive determination of l-dopa.

PubMed

Palakollu, Venkata Narayana; Thapliyal, Neeta; Chiwunze, Tirivashe E; Karpoormath, Rajshekhar; Karunanidhi, Sivanandhan; Cherukupalli, Srinivasulu

2017-08-01

A facile preparation strategy based on electrochemical technique for the fabrication of glycine (Poly-Gly) and electrochemically reduced graphene oxide (ERGO) composite modified electrode was developed. The morphology of the developed composite (ERGO/Poly-Gly) was investigated using field emission scanning electron microscope (FE-SEM). The composite modified glassy carbon electrode (GCE) was characterized using fourier transform-infrared (FT-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The electrochemical characterization results revealed that ERGO/Poly-Gly modified GCE has excellent electrocatalytic activity. Further, it was employed for sensing of l-dopa in pH5.5. Differential pulse voltammetry (DPV) was used for the quantification of l-dopa as well as for the simultaneous resolution of l-dopa and uric acid (UA). The LOD (S/N=3) was found to be 0.15μM at the proposed composite modified electrode. Determination of l-dopa could also be achieved in the presence of potentially interfering substances. The sensor showed high sensitivity and selectivity with appreciable reliability and precision. The proposed sensor was also successfully applied for real sample analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrosynthesis of vanillin from isoeugenol using platinum electrode

NASA Astrophysics Data System (ADS)

Mubarok, H.; Hilyatudini; Saepudin, E.; Ivandini, T. A.

2017-04-01

Vanillin was synthesized from isoeugenol through electrochemical method in one compartment cell using platinum electrode. Cyclic voltammetry in 0.1 M TBAP in methanol and acetonitrile indicated the first oxidation potential at +0.21 and +0.16 V (vs. Ag/AgCl), respectively. Isoeugenolis was proposed to undergo the oxidation accompanied by oxidative cleavage of alkene bond into aldehyde. Accordingly, the synthesis of vanillin was conducted using chronoamperometry technique. The electrosynthesis result was analyzed by HPLC and GC/MS. The optimum condition of the oxidation potential, solvent ratio, time of electrolysis and amount of water was investigated.

Immunosensor based on electrodeposition of gold-nanoparticles and ionic liquid composite for detection of Salmonella pullorum.

PubMed

Wang, Dan; Dou, Wenchao; Zhao, Guangying; Chen, Yan

2014-11-01

In order to increase the reproducibility and stability of electrochemical immunosensor, which is a key issue for its application and popularization, an accurate and stable immunosensor for rapid detection of Salmonella pullorum (S. pullorum) was proposed in this study. The immunosensor was fabricated by modifying Screen-printed Carbon Electrode (SPCE) with electrodeposited gold nanoparticles (AuNPs), HRP-labeled anti-S. pullorum and ionic liquids (ILs) (AuNP/HRP/IL). AuNPs are electrodeposited on the working electrode surface to increase the amount of antibodies that bind to the electrode and then modified with ILs to protect the antibodies from being inactivated in the test environment and maintain their biological activity and the stability of the detection electrode. The electrochemical characteristics of the stepwise modified electrodes and the detection of S. pullorum were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). As shown in the results of the experiments, AuNPs with unique electrochemical properties as well as biocompatibility characteristics have been proven to be able to strengthen the antibody combination effectively and to increase the electrochemical response signal. In addition, a crucial assessment regarding implementation of stability and reproducibility analysis of a range of immunosensors is provided. We found that application of AuNPs/ILs in the immune modified electrodes showed obvious improvement when compared with other groups. Given their high levels of reproducibility, stability, target specificity and sensitivity, AuNPs and ILs were considered to be excellent elements for electrode modification. Copyright © 2014 Elsevier B.V. All rights reserved.

A self-assembled 2D/2D-type protonated carbon nitride-modified graphene oxide nanocomposite with improved photocatalytic activity

NASA Astrophysics Data System (ADS)

Xie, Linfang; Ni, Jie; Tang, Bo; He, Guangyu; Chen, Haiqun

2018-03-01

A surface charge modified g-C3N4 was successfully prepared by protonation of nitric acid. Combination of the protonated g-C3N4 (pCN) and graphene oxide (GO) layers created a 2D/2D-type composite (pCN/GO) under the synergistic effect of sonication-exfoliation and self-assembly. The obtained 2D nanostructure of pCN/GO was explored by electron microscopy analysis. The photocatalytic degradation of rhodamine B (RhB) and ciprofloxacin (CIP) showed a distinctly high efficiency of pCN/GO-5% with excellent stability, which is superior not only to that of g-C3N4, pCN and g-C3N4/GO-5% nanocomposites we prepared, but also to what was reported previously. The optimized combination of GO and pCN afforded the pCN/GO composite intimate interfacial contact within the heterojunction, which promoted the separation of photogenerated electron-hole pairs as evidenced by zeta potential, photoluminescence and photocurrent measurements. A visible-light photocatalytic degradation mechanism associated with pCN/GO nanocomposites was also proposed.

Extraction of Carbon Dioxide and Hydrogen from Seawater by an Electrochemical Acidification Cell. Part 4. Electrode Compartments of Cell Modified and Tested in Scaled-Up Mobile Unit

DTIC Science & Technology

2013-09-03

Electrochemical Acidification Cell Part IV: Electrode Compartments of Cell Modified and Tested in Scaled-Up Mobile Unit September 3, 2013 Approved for public...OF ABSTRACT Extraction of Carbon Dioxide and Hydrogen from Seawater by an Electrochemical Acidification Cell Part IV: Electrode Compartments of Cell...Electrochemical acidification cell Carbon dioxide Hydrogen Polarity reversal An electrochemical acidification cell was scaled-up and integrated into a

Microplasmas for chemical analysis: analytical tools or research toys?

NASA Astrophysics Data System (ADS)

Karanassios, Vassili

2004-07-01

An overview of the activities of the research groups that have been involved in fabrication, development and characterization of microplasmas for chemical analysis over the last few years is presented. Microplasmas covered include: miniature inductively coupled plasmas (ICPs); capacitively coupled plasmas (CCPs); microwave-induced plasmas (MIPs); a dielectric barrier discharge (DBD); microhollow cathode discharge (MCHD) or microstructure electrode (MSE) discharges, other microglow discharges (such as those formed between "liquid" electrodes); microplasmas formed in micrometer-diameter capillary tubes for gas chromatography (GC) or high-performance liquid chromatography (HPLC) applications, and a stabilized capacitive plasma (SCP) for GC applications. Sample introduction into microplasmas, in particular, into a microplasma device (MPD), battery operation of a MPD and of a mini- in-torch vaporization (ITV) microsample introduction system for MPDs, and questions of microplasma portability for use on site (e.g., in the field) are also briefly addressed using examples of current research. To emphasize the significance of sample introduction into microplasmas, some previously unpublished results from the author's laboratory have also been included. And an overall assessment of the state-of-the-art of analytical microplasma research is provided.

Ultrasound assisted synthesis, characterization and electrochemical study of a tetradentate oxovanadium diazomethine complex

NASA Astrophysics Data System (ADS)

Merzougui, Moufida; Ouari, Kamel; Weiss, Jean

2016-09-01

The oxovanadium (IV) complex ;VOL; of a tetradentate Schiff base ligand derived from the condensation of diaminoethane and 2-hydroxy-1-naphthaldehyde was efficiently prepared via ultrasound irradiation and the template effect of VO(acac)2. The resulting product was characterized by elemental analysis, infrared, electronic absorption and molar conductance measurement. Single X-ray structure analysis showed that the complex is a monomeric five-coordinate with a distorted square pyramidal geometry. It crystallizes in monoclinic system having unit cell parameters a = 8.3960 (5) Å; b = 12.5533 (8) Å and c = 18.7804 (11) Å; α = γ = 90°; β = 104.843°(2), with P 21/c space group. Cyclic voltammetry of the complex, carried out on a glassy carbon (GC) electrode in DMF, showed reversible cyclic voltammograms response in the potential range 0.15-0.60 V involving a single electron redox wave VV/VIV, the diffusion coefficient is determinedusing GC rotating disk electrode. The Levich plot Ilim = f(ω1/2), was used to calculate the diffusion-convection controlled currents.

Electrochemical sensor for hazardous food colourant quinoline yellow based on carbon nanotube-modified electrode.

PubMed

Zhao, Jun; Zhang, Yu; Wu, Kangbing; Chen, Jianwei; Zhou, Yikai

2011-09-15

A novel electrochemical method using multi-wall carbon nanotube (MWNT) film-modified electrode was developed for the detection of quinoline yellow. In pH 8 phosphate buffer, an irreversible oxidation peak at 0.71V was observed for quinoline yellow. Compared with the unmodified electrode, the MWNT film-modified electrode greatly increases the oxidation peak current of quinoline yellow, showing notable enhancement effect. The effects of pH value, amount of MWNT, accumulation potential and time were studied on the oxidation peak current of quinoline yellow. The linear range is from 0.75 to 20mgL(-1), and the limit of detection is 0.5mgL(-1). It was applied to the detection of quinoline yellow in commercial soft drinks, and the results consisted with the value that obtained by high-performance liquid chromatography. Copyright © 2011 Elsevier Ltd. All rights reserved.

Electrosorption of a modified electrode in the vicinity of phase transition: A Monte Carlo study

NASA Astrophysics Data System (ADS)

Gavilán Arriazu, E. M.; Pinto, O. A.

2018-03-01

We present a Monte Carlo study for the electrosorption of an electroactive species on a modified electrode. The surface of the electrode is modified by the irreversible adsorption of a non-electroactive species which is able to block a percentage of the adsorption sites. This generates an electrode with variable connectivity sites. A second species, electroactive in this case, is adsorbed in surface vacancies and can interact repulsively with itself. In particular, we are interested in the analysis of the effect of the non-electroactive species near of critical regime, where the c(2 × 2) structure is formed. Lattice-gas models and Monte Carlo simulations in the Gran Canonical Ensemble are used. The analysis conducted is based on the study of voltammograms, order parameters, isotherms, configurational entropy per site, at several values of energies and coverage degrees of the non-electroactive species.

ITO Modification for Efficient Inverted Organic Solar Cells.

PubMed

Susarova, Diana K; Akkuratov, Alexander V; Kukharenko, Andrey I; Cholakh, Seif O; Kurmaev, Ernst Z; Troshin, Pavel A

2017-10-03

We demonstrate a facile approach to designing transparent electron-collecting electrodes by depositing thin layers of medium and low work function metals on top of transparent conductive metal oxides (TCOs) such as ITO and FTO. The modified electrodes were fairly stable for months under ambient conditions and maintained their electrical characteristics. XPS spectroscopy data strongly suggested integration of the deposited metal in the TCO structure resulting in additional doping of the conducting oxide at the interface. Kelvin probe microscopy measurements revealed a significant decrease in the ITO work function after modification. Organic solar cells based on three different conjugated polymers have demonstrated state of the art performances in inverted device geometry using Mg- or Yb-modified ITO as electron collecting electrode. The simplicity of the proposed approach and the excellent ambient stability of the modified ITO electrodes allows one to expect their wide utilization in research laboratories and electronic industry.

Direct determination of creatinine based on poly(ethyleneimine)/phosphotungstic acid multilayer modified electrode.

PubMed

Han, Ping; Xu, Shimei; Feng, Shun; Hao, Yanjun; Wang, Jide

2016-05-01

In this work, the direct determination of creatinine was achieved using a poly(ethyleneimine)/phosphotungstic acid multilayer modified electrode with the assistance of Copper(II) ions by cyclic voltammetry. The quantity of creatinine were determined by measuring the redox peak current of Cu(II)-creatinine complex/Cu(I)-creatinine complex. Factors affecting the response current of creatinine at the modified electrode were optimized. A linear relationship between the response current and the concentration of creatinine ranging from 0.125 to 62.5μM was obtained with a detection limit of 0.06μM. The proposed method was applied to determine creatinine in human urine, and satisfied results were gotten which was validated in accordance with high performance liquid chromatography. The proposed electrode provided a promising alternative in routine sensing for creatinine without enzymatic assistance. Copyright © 2016 Elsevier B.V. All rights reserved.

Flow injection amperometric detection of insulin at cobalt hydroxide nanoparticles modified carbon ceramic electrode.

PubMed

Habibi, Esmaeil; Omidinia, Eskandar; Heidari, Hassan; Fazli, Maryam

2016-02-15

Cobalt hydroxide nanoparticles were prepared onto a carbon ceramic electrode (CHN|CCE) using the cyclic voltammetry (CV) technique. The modified electrode was characterized by X-ray diffraction and scanning electron microscopy. The results showed that CHN with a single-layer structure was uniformly electrodeposited on the surface of CCE. The electrocatalytic activity of the modified electrode toward the oxidation of insulin was studied by CV. CHN|CCE was also used in a homemade flow injection analysis system for insulin determination. The limit of detection (signal/noise [S/N] = 3) and sensitivity were found to be 0.11 nM and 11.8 nA/nM, respectively. Moreover, the sensor was used for detection of insulin in human serum samples. This sensor showed attractive properties such as high stability, reproducibility, and high selectivity. Copyright © 2015 Elsevier Inc. All rights reserved.

Novel Signal-Amplified Fenitrothion Electrochemical Assay, Based on Glassy Carbon Electrode Modified with Dispersed Graphene Oxide

NASA Astrophysics Data System (ADS)

Wang, Limin; Dong, Jinbo; Wang, Yulong; Cheng, Qi; Yang, Mingming; Cai, Jia; Liu, Fengquan

2016-03-01

A novel signal-amplified electrochemical assay for the determination of fenitrothion was developed, based on the redox behaviour of organophosphorus pesticides on a glassy carbon working electrode. The electrode was modified using graphene oxide dispersion. The electrochemical response of fenitrothion at the modified electrode was investigated using cyclic voltammetry, current-time curves, and square-wave voltammetry. Experimental parameters, namely the accumulation conditions, pH value, and volume of dispersed material, were optimised. Under the optimum conditions, a good linear relationship was obtained between the oxidation peak current and the fenitrothion concentration. The linear range was 1-400 ng·mL-1, with a detection limit of 0.1 ng·mL-1 (signal-to-nose ratio = 3). The high sensitivity of the sensor was demonstrated by determining fenitrothion in pakchoi samples.

BIOSENSOR FOR DIRECT DETERMINATION OF ORGANOPHOSPHATE NERVE AGENTS. 1. POTENTIOMETRIC ENZYME ELECTRODE. (R823663)

EPA Science Inventory

A potentiometric enzyme electrode for the direct measurement of organophosphate (OP)
nerve agents was developed. The basic element of this enzyme electrode was a pH electrode
modified with an immobilized organophosphorus hydrolase (OPH) layer formed by cross-linking
OPH ...

Chemically modified graphene based supercapacitors for flexible and miniature devices

NASA Astrophysics Data System (ADS)

Ghosh, Debasis; Kim, Sang Ouk

2015-09-01

Rapid progress in the portable and flexible electronic devises has stimulated supercapacitor research towards the design and fabrication of high performance flexible devices. Recent research efforts for flexible supercapacitor electrode materials are highly focusing on graphene and chemically modified graphene owing to the unique properties, including large surface area, high electrical and thermal conductivity, excellent mechanical flexibility, and outstanding chemical stability. This invited review article highlights current status of the flexible electrode material research based on chemically modified graphene for supercapacitor application. A variety of electrode architectures prepared from chemically modified graphene are summarized in terms of their structural dimensions. Novel prototypes for the supercapacitor aiming at flexible miniature devices, i.e. microsupercapacitor with high energy and power density are highlighted. Future challenges relevant to graphene-based flexible supercapacitors are also suggested. [Figure not available: see fulltext.

Hierarchical structured Sm2O3 modified CuO nanoflowers as electrode materials for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Zhang, Xiaojuan; He, Mingqian; He, Ping; Liu, Hongtao; Bai, Hongmei; Chen, Jingchao; He, Shaoying; Zhang, Xingquan; Dong, Faqing; Chen, Yang

2017-12-01

By a simple and cost effective chemical precipitation-hydrothermal method, novel hierarchical structured Sm2O3 modified CuO nanoflowers are prepared and investigated as electrode materials for supercapacitors. The physical properties of prepared materials are characterized by XRD, FE-SEM, EDX and FTIR techniques. Furthermore, electrochemical performances of prepared materials are investigated by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectrum in 1.0 M KOH electrolyte. The resulting Sm2O3 modified CuO based electrodes exhibit obviously enhanced capacitive properties owing to the unique nanostructures and strong synergistic effects. It is worth noting that the optimized SC-3 based electrode exhibits the best electrochemical performances in all prepared electrodes, including higher specific capacitance (383.4 F g-1 at 0.5 A g-1) and good rate capability (393.2 F g-1 and 246.3 F g-1 at 0.3 A g-1 and 3.0 A g-1, respectively), as well as excellent cycling stability (84.6% capacitance retention after 2000 cycles at 1.0 A g-1). The present results show that Sm2O3 is used as a promising modifier to change the morphology and improve electrochemical performances of CuO materials.

Zeolite A functionalized with copper nanoparticles and graphene oxide for simultaneous electrochemical determination of dopamine and ascorbic acid.

PubMed

He, Ping; Wang, Wei; Du, Licheng; Dong, Faqin; Deng, Yuequan; Zhang, Tinghong

2012-08-20

A novel Cu-zeolite A/graphene modified glassy carbon electrode for the simultaneous electrochemical determination of dopamine (DA) and ascorbic acid (AA) has been described. The Cu-zeolite A/graphene composites were prepared using Cu(2+) functionalized zeolite A and graphene oxide as the precursor, and subsequently reduced by chemical agents. The composites were characterized by X-ray diffraction, Fourier transform infrared spectra and scanning electron microscopy. Based on the Cu-zeolite A/graphene-modified electrode, the potential difference between the oxidation peaks of DA and AA was over 200mV, which was adequate for the simultaneous electrochemical determination of DA and AA. Also the proposed Cu-zeolite/graphene-modified electrode showed higher electrocatalytic performance than zeolite/graphene electrode or graphene-modified electrode. The electrocatalytic oxidation currents of DA and AA were linearly related to the corresponding concentration in the range of 1.0×10(-7)-1.9×10(-5)M for DA and 2.0×10(-5)-2.0×10(-4)M for AA. Detection limits (S/N=3) were estimated to be 4.1×10(-8)M for DA and 1.1×10(-5)M for AA, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

IMPACT OF POLYCYCLIC AROMATIC HYDROCARBONS OF THE ELECTROCHEMICAL RESPONSES OF A FERRICYNIDE PROBE AT TEMPLATE-MODIFIED SELF ASSEMBLED MONOLAYERS ON GOLD ELECTRODES

EPA Science Inventory

The impact of pyrene on the electrochemical response of the ferricyanide probe using Self Assembled Monolayer (SAM)-modified gold electrodes was investigated using Cyclic Voltammetry (CV) and Square Wave Voltammetry (SWV). These results suggest the feasibility of using SAMs, par...

Double-Polymer-Modified Pencil Lead for Stripping Voltammetry of Perchlorate in Drinking Water

ERIC Educational Resources Information Center

Izadyar, Anahita; Kim, Yushin; Ward, Michelle M.; Amemiya, Shigeru

2012-01-01

The inexpensive and disposable electrode based on a double-polymer-modified pencil lead is proposed for upper-division undergraduate instrumental laboratories to enable the highly sensitive detection of perchlorate. Students fabricate and utilize their own electrodes in the 3-4 h laboratory session to learn important concepts and methods of…

A Facile Electrochemical Preparation of Reduced Graphene Oxide@Polydopamine Composite: A Novel Electrochemical Sensing Platform for Amperometric Detection of Chlorpromazine

NASA Astrophysics Data System (ADS)

Palanisamy, Selvakumar; Thirumalraj, Balamurugan; Chen, Shen-Ming; Wang, Yi-Ting; Velusamy, Vijayalakshmi; Ramaraj, Sayee Kannan

2016-09-01

We report a novel and sensitive amperometric sensor for chlorpromazine (CPZ) based on reduced graphene oxide (RGO) and polydopamine (PDA) composite modified glassy carbon electrode. The RGO@PDA composite was prepared by electrochemical reduction of graphene oxide (GO) with PDA. The RGO@PDA composite modified electrode shows an excellent electro-oxidation behavior to CPZ when compared with other modified electrodes such as GO, RGO and GO@PDA. Amperometric i-t method was used for the determination of CPZ. Amperometry result shows that the RGO@PDA composite detects CPZ in a linear range from 0.03 to 967.6 μM. The sensor exhibits a low detection limit of 0.0018 μM with the analytical sensitivity of 3.63 ± 0.3 μAμM-1 cm-2. The RGO@PDA composite shows its high selectivity towards CPZ in the presence of potentially interfering drugs such as metronidazole, phenobarbital, chlorpheniramine maleate, pyridoxine and riboflavin. In addition, the fabricated RGO@PDA modified electrode showed an appropriate recovery towards CPZ in the pharmaceutical tablets.

Simulating Charge Transport in Solid Oxide Mixed Ionic and Electronic Conductors: Nernst-Planck Theory vs Modified Fick's Law

DOE PAGES

Jin, Xinfang; White, Ralph E.; Huang, Kevin

2016-10-04

With the assumption that the Fermi level (electrochemical potential of electrons) is uniform across the thickness of a mixed ionic and electronic conducting (MIEC) electrode, the charge-transport model in the electrode domain can be reduced to the modified Fick’s first law, which includes a thermodynamic factor A. A transient numerical solution of the Nernst-Planck theory was obtained for a symmetric cell with MIEC electrodes to illustrate the validity of the assumption of a uniform Fermi level. Subsequently, an impedance numerical solution based on the modified Fick’s first law is compared with that from the Nernst-Planck theory. The results show thatmore » Nernst-Planck charge-transport model is essentially the same as the modified Fick’s first law model as long as the MIEC electrodes have a predominant electronic conductivity. However, because of the invalidity of the uniform Fermi level assumption for aMIEC electrolyte with a predominant ionic conductivity, Nernst-Planck theory is needed to describe the charge transport behaviors.« less

Electrochemical behavior and voltammetric determination of acetaminophen based on glassy carbon electrodes modified with poly(4-aminobenzoic acid)/electrochemically reduced graphene oxide composite films.

PubMed

Zhu, Wencai; Huang, Hui; Gao, Xiaochun; Ma, Houyi

2014-12-01

Poly(4-aminobenzoic acid)/electrochemically reduced graphene oxide composite film modified glassy carbon electrodes (4-ABA/ERGO/GCEs) were fabricated by a two-step electrochemical method. The electrochemical behavior of acetaminophen at the modified electrode was investigated by means of cyclic voltammetry. The results indicated that 4-ABA/ERGO composite films possessed excellent electrocatalytic activity towards the oxidation of acetaminophen. The electrochemical reaction of acetaminophen at 4-ABA/ERGO/GCE is proved to be a surface-controlled process involving the same number of protons and electrons. The voltammetric determination of acetaminophen performed with the 4-ABA/ERGO modified electrode presents a good linearity in the range of 0.1-65 μM with a low detection limit of 0.01 μM (S/N=3). In the case of using the 4-ABA/ERGO/GCE, acetaminophen and dopamine can be simultaneously determined without mutual interference. Furthermore, the 4-ABA/ERGO/GCE has good reproducibility and stability, and can be used to determine acetaminophen in tablets. Copyright © 2014 Elsevier B.V. All rights reserved.

Redox electrodes comprised of polymer-modified carbon nanomaterials

NASA Astrophysics Data System (ADS)

Roberts, Mark; Emmett, Robert; Karakaya, Mehmet; Podila, Ramakrishna; Rao, Apparao; Clemson Physics Team; Clemson Chemical Engineering Team

2013-03-01

A shift in how we generate and use electricity requires new energy storage materials and systems compatible with hybrid electric transportation and the integration of renewable energy sources. Supercapacitors provide a solution to these needs by combining the high power, rapid switching, and exceptional cycle life of a capacitor with the high energy density of a battery. Our research brings together nanotechnology and materials chemistry to address the limitations of electrode materials. Paper electrodes fabricated with various forms of carbon nanomaterials, such as nanotubes, are modified with redox-polymers to increase the electrode's energy density while maintaining rapid discharge rates. In these systems, the carbon nanomaterials provide the high surface area, electrical conductivity, nanoscale and porosity, while the redox polymers provide a mechanism for charge storage through Faradaic charge transfer. The design of redox polymers and their incorporation into nanomaterial electrodes will be discussed with a focus on enabling high power and high energy density electrodes.

Surface-modified Mg{sub 2}Ni-type negative electrode materials for Ni-MH battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, N.; Luan, B.; Bradhurst, D.

1997-12-01

In order to further improve the electrode performance of Mg{sub 1.9}Y{sub 0.1}Ni{sub 0.9}Al{sub 0.1} alloy at ambient temperature, its surface was modified by an ultrasound pretreatment in the alkaline solution and microencapsulation with Ni-P coating. The effects of various surface modifications on the microstructure and electrochemical performance of the alloy electrodes were investigated and compared in this paper. It was found that the modification with ultrasound pretreatment significantly improved the electrocatalytic activity of the negative electrode and then reduced the overpotential of charging/discharging, resulting in a remarkable increase of electrode capacity and high-rate discharge capability but having little influence onmore » the cycle life. However, the electrode fabricated from the microencapsulated alloy powder showed a higher discharge capacity, better high-rate discharge capability and longer cycle life as well.« less

Direct electrochemistry with enhanced electrocatalytic activity of hemoglobin in hybrid modified electrodes composed of graphene and multi-walled carbon nanotubes.

PubMed

Sun, Wei; Cao, Lili; Deng, Ying; Gong, Shixing; Shi, Fan; Li, Gaonan; Sun, Zhenfan

2013-06-05

A graphene (GR) and multi-walled carbon nanotubes (MWCNT) hybrid was prepared and modified on a 1-hexylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE). Hemoglobin (Hb) was immobilized on GR-MWCNT/CILE surface with Nafion as the film forming material and the modified electrode was denoted as Nafion/Hb-GR-MWCNT/CILE. Spectroscopic results revealed that Hb molecules retained its native structure in the GR-MWCNT hybird. Electrochemical behaviors of Hb were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks obtained, which indicated that direct electron transfer of Hb was realized in the hybrid modified electrode. The result could be attributed to the synergistic effects of GR-MWCNT hybrid with enlarged surface area and improved conductivity through the formation of a three-dimensional network. Electrochemical parameters of the immobilized Hb on the electrode surface were further calculated with the results of the electron transfer number (n) as 1.03, the charge transfer coefficient (a) as 0.58 and the electron-transfer rate constant (ks) as 0.97 s(-1). The Hb modified electrode showed good electrocatalytic ability toward the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.05 to 38.0 mmol L(-1) with a detection limit of 0.0153 mmol L(-1) (3σ), H2O2 in the concentration range from 0.1 to 516.0 mmol L(-1) with a detection limit of 34.9 nmol/L (3σ) and NaNO2 in the concentration range from 0.5 to 650.0 mmol L(-1) with a detection limit of 0.282 μmol L(-1) (3σ). So the proposed electrode had the potential application in the third-generation electrochemical biosensors without mediator. Copyright © 2013 Elsevier B.V. All rights reserved.

Amperometric biosensor based on glassy carbon electrode modified with long-length carbon nanotube and enzyme

NASA Astrophysics Data System (ADS)

Furutaka, Hajime; Nemoto, Kentaro; Inoue, Yuki; Hidaka, Hiroki; Muguruma, Hitoshi; Inoue, Hitoshi; Ohsawa, Tatsuya

2016-05-01

An amperometric biosensor based on a glassy carbon electrode modified with long-length multiwalled carbon nanotubes (MWCNTs) and enzyme nicotinamide-adenine-dinucleotide-dependent glucose dehydrogenase (GDH) is presented. We demonstrate the effect of the MWCNT length on the amperometric response of the enzyme biosensor. The long length of MWCNT is 200 µm (average), whereas the normal length of MWCNT is 1 µm (average). The response of the long MWCNT-GDH electrode is 2 times more sensitive than that of the normal-length MWCNT-GDH electrode in the concentration range from 0.25-35 mM. The result of electrochemical impedance spectroscopy measurements suggest that the long-length MWCNT-GDH electrode formed a better electron transfer network than the normal-length one.

High-performance supercapacitors based on poly(ionic liquid)-modified graphene electrodes.

PubMed

Kim, Tae Young; Lee, Hyun Wook; Stoller, Meryl; Dreyer, Daniel R; Bielawski, Christopher W; Ruoff, Rodney S; Suh, Kwang S

2011-01-25

We report a high-performance supercapacitor incorporating a poly(ionic liquid)-modified reduced graphene oxide (PIL:RG-O) electrode and an ionic liquid (IL) electrolyte (specifically, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide or EMIM-NTf(2)). PIL:RG-O provides enhanced compatibility with the IL electrolyte, thereby increasing the effective electrode surface area accessible to electrolyte ions. The supercapacitor assembled with PIL:RG-O electrode and EMIM-NTf(2) electrolyte showed a stable electrochemical response up to 3.5 V operating voltage and was capable of yielding a maximum energy density of 6.5 W·h/kg with a power density of 2.4 kW/kg. These results demonstrate the potential of the PIL:RG-O material as an electrode in high-performance supercapacitors.

Selective determination of four arsenic species in rice and water samples by modified graphite electrode-based electrolytic hydride generation coupled with atomic fluorescence spectrometry.

PubMed

Yang, Xin-An; Lu, Xiao-Ping; Liu, Lin; Chi, Miao-Bin; Hu, Hui-Hui; Zhang, Wang-Bing

2016-10-01

This work describes a novel non-chromatographic approach for the accurate and selective determining As species by modified graphite electrode-based electrolytic hydride generation (EHG) for sample introduction coupled with atomic fluorescence spectrometry (AFS) detection. Two kinds of sulfydryl-containing modifiers, l-cysteine (Cys) and glutathione (GSH), are used to modify cathode. The EHG performance of As has been changed greatly at the modified cathode, which has never been reported. Arsenite [As(III)] on the GSH modified graphite electrode (GSH/GE)-based EHG can be selectively and quantitatively converted to AsH3 at applied current of 0.4A. As(III) and arsenate [As(V)] on the Cys modified graphite electrode (Cys/GE) EHG can be selectively and efficiently converted to arsine at applied current of 0.6A, whereas monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) do not form any or only less volatile hydrides under this condition. By changing the analytical conditions, we also have achieved the analysis of total As (tAs) and DMA. Under the optimal condition, the detection limits (3s) of As(III), iAs and tAs in aqueous solutions are 0.25μgL(-1), 0.22μgL(-1) and 0.10μgL(-1), respectively. The accuracy of the method is verified through the analysis of standard reference materials (SRM 1568a). Copyright © 2016 Elsevier B.V. All rights reserved.

Graphene-loaded nanofiber-modified electrodes for the ultrasensitive determination of dopamine.

PubMed

Rodthongkum, Nadnudda; Ruecha, Nipapan; Rangkupan, Ratthapol; Vachet, Richard W; Chailapakul, Orawon

2013-12-04

A novel and highly sensitive electrochemical system based on electrospun graphene/polyaniline/polystyrene (G/PANI/PS) nanofiber-modified screen-printed carbon electrodes has been developed for dopamine (DA) determination. A dramatic increase (9 times) in the current signal for the redox reaction of a standard, ferri/ferrocyanide [Fe(CN)6](3-/4-) couple was found when compared to an unmodified electrode. This modified electrode also exhibited favorable electron transfer kinetics and excellent electrocatalytic activity toward the oxidation of DA. When used together with square wave voltammetry (SWV), DA can be selectively determined in the presence of the common interferents (i.e. ascorbic acid and uric acid). Under optimal conditions, a very low limit of detection (0.05 nM) and limit of quantification (0.30 nM) were achieved for DA. In addition, a wide dynamic range of 0.1 nM to 100 μM was found for this electrode system. Finally, the system can be successfully applied to determine DA in complex biological environment (e.g. human serum, urine) with excellent reproducibility. Copyright © 2013 Elsevier B.V. All rights reserved.

Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

NASA Technical Reports Server (NTRS)

Rosario-Castro, Belinda I.; Fachini, Estevao R.; Contes, Enid J.; Perez-Davis, Marla E.; Cabrera, Carlos R.

2008-01-01

Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

The electrochemical performance of graphene modified electrodes: an analytical perspective.

PubMed

Brownson, Dale A C; Foster, Christopher W; Banks, Craig E

2012-04-21

We explore the use of graphene modified electrodes towards the electroanalytical sensing of various analytes, namely dopamine hydrochloride, uric acid, acetaminophen and p-benzoquinone via cyclic voltammetry. In line with literature methodologies and to investigate the full-implications of employing graphene in this electrochemical context, we modify electrode substrates that exhibit either fast or slow electron transfer kinetics (edge- or basal- plane pyrolytic graphite electrodes respectively) with well characterised commercially available graphene that has not been chemically treated, is free from surfactants and as a result of its fabrication has an extremely low oxygen content, allowing the true electroanalytical applicability of graphene to be properly de-convoluted and determined. In comparison to the unmodified underlying electrode substrates (constructed from graphite), we find that graphene exhibits a reduced analytical performance in terms of sensitivity, linearity and observed detection limits towards each of the various analytes studied within. Owing to graphene's structural composition, low proportion of edge plane sites and consequent slow heterogeneous electron transfer rates, there appears to be no advantages, for the analytes studied here, of employing graphene in this electroanalytical context.

Pencil Graphite Electrodes: A Versatile Tool in Electroanalysis

PubMed Central

2017-01-01

Due to their electrochemical and economical characteristics, pencil graphite electrodes (PGEs) gained in recent years a large applicability to the analysis of various types of inorganic and organic compounds from very different matrices. The electrode material of this type of working electrodes is constituted by the well-known and easy commercially available graphite pencil leads. Thus, PGEs are cheap and user-friendly and can be employed as disposable electrodes avoiding the time-consuming step of solid electrodes surface cleaning between measurements. When compared to other working electrodes PGEs present lower background currents, higher sensitivity, good reproducibility, and an adjustable electroactive surface area, permitting the analysis of low concentrations and small sample volumes without any deposition/preconcentration step. Therefore, this paper presents a detailed overview of the PGEs characteristics, designs and applications of bare, and electrochemically pretreated and chemically modified PGEs along with the corresponding performance characteristics like linear range and detection limit. Techniques used for bare or modified PGEs surface characterization are also reviewed. PMID:28255500

Facile synthesis of NiAl-layered double hydroxide/graphene hybrid with enhanced electrochemical properties for detection of dopamine

NASA Astrophysics Data System (ADS)

Li, Meixia; Zhu, Jun E.; Zhang, Lili; Chen, Xu; Zhang, Huimin; Zhang, Fazhi; Xu, Sailong; Evans, David G.

2011-10-01

Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clays, have been investigated widely as promising electrochemical active materials. Due to the inherently weak conductivity, the electrochemical properties of LDHs were improved typically by utilization of either functional molecules intercalated between LDH interlayer galleries, or proteins confined between exfoliated LDH nanosheets. Here, we report a facile protocol to prepare NiAl-LDH/graphene (NiAl-LDH/G) nanocomposites using a conventional coprecipitation process under low-temperature conditions and subsequent reduction of the supporting graphene oxide. Electrochemical tests showed that the NiAl-LDH/G modified electrode exhibited highly enhanced electrochemical performance of dopamine electrooxidation in comparison with the pristine NiAl-LDH modified electrode. Results of high-resolution transmission electron microscopy and Raman spectra provide convincing information on the nanostructure and composition underlying the enhancement. Our results of the NiAl-LDH/G modified electrodes with the enhanced electrochemical performance may allow designing a variety of promising hybrid sensors via a simple and feasible approach.Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clays, have been investigated widely as promising electrochemical active materials. Due to the inherently weak conductivity, the electrochemical properties of LDHs were improved typically by utilization of either functional molecules intercalated between LDH interlayer galleries, or proteins confined between exfoliated LDH nanosheets. Here, we report a facile protocol to prepare NiAl-LDH/graphene (NiAl-LDH/G) nanocomposites using a conventional coprecipitation process under low-temperature conditions and subsequent reduction of the supporting graphene oxide. Electrochemical tests showed that the NiAl-LDH/G modified electrode exhibited highly enhanced electrochemical performance of dopamine electrooxidation in comparison with the pristine NiAl-LDH modified electrode. Results of high-resolution transmission electron microscopy and Raman spectra provide convincing information on the nanostructure and composition underlying the enhancement. Our results of the NiAl-LDH/G modified electrodes with the enhanced electrochemical performance may allow designing a variety of promising hybrid sensors via a simple and feasible approach. Electronic supplementary information (ESI) available: Fig. S1 showing 2D fast Fourier transform (FFT) image of NiAl-LDH phase in NiAl-LDH/G composites, and Fig. S2 showing CV curve of the pristine G modified electrode. See DOI: 10.1039/c1nr10592b.

A comparison of the in vitro cytotoxicity of conventional and resin modified glass ionomer cements

PubMed Central

Selimović-Dragaš, Mediha; Huseinbegović, Amina; Kobašlija, Sedin; Hatibović-Kofman, Šahza

2012-01-01

To evaluate cytotoxicity of experimental conventional and resin modified glass-ionomer cements on UMR-106 osteoblast cell cultures and cell cultures of NIH3T3 mouse fibroblasts specimens were prepared for every experimental material and divided into: group 1. Conventional glass-ionomer cements: GC Fuji IX GP Fast, GC Fuji Triage and Ketac Silver; group 2. Resin modified glass-ionomer cements: GC Fuji II LC, GC Fuji Plus and Vitrebond; group 3. Positive control was presented by specimens of composite Vit-l-ecence® and negative control-group 4. was presented by α-minimum essential medium for UMR-106 – osteoblast-like cells and Dulbecco’s Modified Eagle’s Medium for NIH3T3 mouse fibroblast cells. Both cell cultures were exposed to 10% of eluate of each single specimen of each experimental material. Experimental dishes were incubated for 24 h. Cell metabolism was evaluated using methyltetrazolium assay. Kruskal-Wallis test and Tukey-Kramer post hoc test for the materials evaluated on NIH3T3 mouse fibroblast cells, as well as UMR-106 osteoblast-like cells showed significantly more cytotoxicity of RMGICs, predominantly Vitrebond to both GICs and composite-Vit-l-ecence®. The lowest influence on cell’s metabolism on UMR-106 osteoblas-like cells was shown by Ketac Silver and the lowest influence on cell’s metabolism on NIH3T3 mouse fibroblast cells was shown by Fuji IX GP Fast. Statistical evaluation of sensitivity of cell lines UMR-106 osteoblast-like cells and NIH3T3 mouse fibroblast cells, using Mann-Whitney test, showed that NIH3T3 mouse fibroblast cells were more sensitive for the evaluation of cytotoxicity of dental materials. PMID:23198945

Design of ultrasensitive bisphenol A-aptamer based on platinum nanoparticles loading to polyethyleneimine-functionalized carbon nanotubes.

PubMed

Derikvandi, Zeinab; Abbasi, Amir Reza; Roushani, Mahmoud; Derikvand, Zohreh; Azadbakht, Azadeh

2016-11-01

Here, a highly sensitive electrochemical aptasensor based on a novel signal amplification strategy for the determination of bisphenol A (BPA) was developed. Construction of the aptasensor began with the deposition of highly dispersed platinum nanoparticles (PtNPs)/acid-oxidized carbon nanotubes (CNTs-COOH) functionalized with polyethyleneimine (PEI) at the surface of glassy carbon (PtNPs/PEI/CNTs-COOH/GC) electrode. After immobilizing the amine-capped capture probe (ssDNA1) through the covalent amide bonds formed by the carboxyl groups on the nanotubes and the amino groups on the oligonucleotides, we employed a designed complementary BPA-aptamer (ssDNA2) as a detection probe to hybridize with the ssDNA1. By adding BPA as a target, the aptamer specifically bound to BPA and its end folded into a BPA-binding junction. Because of steric/conformational restrictions caused by aptamer-BPA complex formation at the surface of modified electrode, the interfacial electron transfer of [Fe(CN)6](3-/4-) as a probe was blocked. Sensitive quantitative detection of BPA was carried out by monitoring the decrease of differential pulse voltammetric responses of [Fe(CN)6](3-/4-) peak current with increasing BPA concentrations. The newly developed aptasensor embraced a number of attractive features such as ease of fabrication, low detection limit, excellent selectivity, good stability and a wide linear range with respect to BPA. Copyright © 2016 Elsevier Inc. All rights reserved.

Synthesis, characterization and antibacterial activity of superparamagnetic nanoparticles modified with glycol chitosan

NASA Astrophysics Data System (ADS)

Inbaraj, Baskaran Stephen; Tsai, Tsung-Yu; Chen, Bing-Huei

2012-02-01

Iron oxide nanoparticles (IONPs) were synthesized by coprecipitation of iron salts in alkali media followed by coating with glycol chitosan (GC-coated IONPs). Both bare and GC-coated IONPs were subsequently characterized and evaluated for their antibacterial activity. Comparison of Fourier transform infrared spectra and thermogravimetric data of bare and GC-coated IONPs confirmed the presence of GC coating on IONPs. Magnetization curves showed that both bare and GC-coated IONPs are superparamagnetic and have saturation magnetizations of 70.3 and 59.8 emu g-1, respectively. The IONP size was measured as ~8-9 nm by transmission electron microscopy, and their crystal structure was assigned to magnetite from x-ray diffraction patterns. Both bare and GC-coated IONPs inhibited the growths of Escherichia coli ATCC 8739 and Salmonella enteritidis SE 01 bacteria better than the antibiotics linezolid and cefaclor, as evaluated by the agar dilution assay. GC-coated IONPs showed higher potency against E. coli O157:H7 and Staphylococcus aureus ATCC 10832 than bare IONPs. Given their biocompatibility and antibacterial properties, GC-coated IONPs are a potential nanomaterial for in vivo applications.

Covalently functionalized single-walled carbon nanotubes and graphene composite electrodes for pseudocapacitor application

NASA Astrophysics Data System (ADS)

Le Barny, Pierre; Servet, Bernard; Campidelli, Stéphane; Bondavalli, Paolo; Galindo, Christophe

2013-09-01

The use of carbon-based materials in electrochemical double-layer supercapacitors (EDLC) is currently being the focus of much research. Even though activated carbon (AC) is the state of the art electrode material, AC suffers from some drawbacks including its limited electrical conductivity, the need for a binder to ensure the expected electrode cohesion and its limited accessibility of its pores to solvated ions of the electrolyte. Owing to their unique physical properties, carbon nanotubes (CNTs) or graphene could overcome these drawbacks. It has been demonstrated that high specific capacitance could be obtained when the carbon accessible surface area of the electrode was finely tailored by using graphene combined with other carbonaceous nanoparticles such as CNTs12.In this work, to further increase the specific capacitance of the electrode, we have covalently grafted onto the surface of single-walled carbon nanotubes (SWCNTs), exfoliated graphite or graphene oxide (GO), anthraquinone (AQ) derivatives which are electrochemically active materials. The modified SWCNTs and graphene-like materials have been characterized by Raman spectroscopy, X-ray photoemission and cyclic voltammetry . Then suspensions based on mixtures of modified SWCNTs and modified graphene-like materials have been prepared and transformed into electrodes either by spray coating or by filtration. These electrodes have been characterized by SEM and by cyclic voltammetry in 0.1M H2S04 electrolyte.

Three-dimensionally ordered macroporous (3DOM) gold-nanoparticle-doped titanium dioxide (GTD) photonic crystals modified electrodes for hydrogen peroxide biosensor.

PubMed

Li, Jianlin; Han, Tao; Wei, Nannan; Du, Jiangyan; Zhao, Xiangwei

2009-12-15

Gold nanoparticles have been introduced into the wall framework of titanium dioxide photonic crystals by the colloidal crystal template technique. The three-dimensionally ordered macroporous gold-nanoparticle-doped titanium dioxide (3DOM GTD) film was modified on the indium-tin oxide (ITO) electrode surface and used for the hydrogen peroxide biosensor. The direct electron transfer and electrocatalysis of horseradish peroxidase (HRP) immobilized on this film have been investigated. The 3DOM GTD film could provide a good microenvironment for retaining the biological bioactivity, large internal area, and superior conductivity. The HRP/3DOM GTD/ITO electrode exhibited two couples of redox peaks corresponding to the HRP intercalated in the mesopores and adsorbed on the external surface of the film with the formal potential of -0.19 and -0.52V in 0.1M PBS (pH 7.4), respectively. The HRP intercalated in the mesopores showed a surface-controlled process with a single proton transfer. The direct electron transfer between the adsorbed HRP and the electrode is achieved without the aid of an electron mediator. The H(2)O(2) biosensor displayed a rapid eletrocatalytic response (less than 3s), a wide linear range from 0.5 microM to 1.4mM with a detection limit of 0.2 microM, high sensitivity (179.9 microAmM(-1)), good stability and reproducibility. Compared with the free-Au doped titanium dioxide photonic crystals modified electrode, the GTD modified electrode could greatly enhance the response current signal, linear detection range and higher sensitivity. The 3DOM GTD provided a new matrix for protein immobilization and direct transfer study and opened a way for low conductivity electrode biosensor.

Role of Au(NPs) in the enhanced response of Au(NPs)-decorated MWCNT electrochemical biosensor

PubMed Central

Mehmood, Shahid; Ciancio, Regina; Carlino, Elvio; Bhatti, Arshad S

2018-01-01

Background The combination of Au-metallic-NPs and CNTs are a new class of hybrid nanomaterials for the development of electrochemical biosensor. Concentration of Au(nanoparticles [NPs]) in the electrochemical biosensor is crucial for the efficient charge transfer between the Au-NPs-MWCNTs modified electrode and electrolytic solution. Methods In this work, the charge transfer kinetics in the glassy carbon electrode (GCE) modified with Au(NPs)–multiwalled carbon nanotube (MWCNT) nanohybrid with varied concentrations of Au(NPs) in the range 40–100 nM was studied using electrochemical impedance spectroscopy (EIS). Field emission scanning electron microscopy and transmission electron microscopy confirmed the attachment of Au(NPs) on the surface of MWCNTs. Results The cyclic voltammetry and EIS results showed that the charge transfer mechanism was diffusion controlled and the rate of charge transfer was dependent on the concentration of Au(NPs) in the nanohybrid. The formation of spherical diffusion zone, which was dependent on the concentration of Au(NPs) in nanohybrids, was attributed to result in 3 times the increase in the charge transfer rate ks, 5 times increase in mass transfer, and 5% (9%) increase in Ipa (Ipc) observed in cyclic voltammetry in 80 nM Au(NP) nanohybrid-modified GCE from MWCNT-modified GCE. The work was extended to probe the effect of charge transfer rates at various concentrations of Au(NPs) in the nanohybrid-modified electrodes in the presence of Escherichia coli. The cyclic voltammetry results clearly showed the best results for 80 nM Au(NPs) in nanohybrid electrode. Conclusion The present study suggested that the formation of spherical diffusion zone in nanohybrid-modified electrodes is critical for the enhanced electrochemical biosensing applications. PMID:29713161

A modified ion-selective electrode method for measurement of chloride in sweat.

PubMed

Finley, P R; Dye, J A; Lichti, D A; Byers, J M; Williams, R J

1978-06-01

A modified method of analysis of sweat chloride concentration with an ion-selective electrode is presented. The original method of sweat chloride analysis proposed by the Orion Research Corporation (Cambridge, Massachusetts 02139) is inadequate because it produces erratic and misleading results. The modified method was compared with the reference quantitative method of Gibson and Cooke. In the modified method, individual electrode pads are cut and placed in the electrodes rather than using the pads supplied by the company; pilocarpine nitrate (2,000 mg/l) is used in place of pilocarpine HCl (640 mg/l); sodium bicarbonate as the weak electrolyte is used instead of K2SO4. A 10-minute period for sweat accumulation is employed rather than a zero-time collection as in the original Orion method. The modification has been studied for reproducibility in individuals, reproducibility between right and left arm in individuals; it has been compared extensively with the quantitative method of Gibson and Cooke, both in normal individuals and in patients with cystic fibrosis. There is excellent agreement between the modified method and the quantitative reference method. There appears to be a slight bias toward higher concentrations of chloride from the right arm compared with the left arm, but this difference is not medically significant.

Electroanalytical and Spectroscopic Studies of Poly(2,2'-bithiophene)-Modified Platinum Electrode to Detect Catechol in the Presence of Ascorbic Acid

ERIC Educational Resources Information Center

Lunsford, Suzanne K.; Speelman, Nicole; Stinson, Jelynn; Yeary, Amber; Choi, Hyeok; Widera, Justyna; Dionysiou, Dionysios D.

2008-01-01

This article describes an undergraduate laboratory for an instrumental analysis course that integrates electroanalytical chemistry and infrared spectroscopy. Modified electrode surfaces are prepared by constant potentiometric electrolysis over the potential range of 1.5-1.8 V and analyzed by cyclic voltammetry and infrared spectroscopy. The…

Modified Carbon Nanotube Paste Electrode for Voltammetric Determination of Carbidopa, Folic Acid, and Tryptophan

PubMed Central

Esfandiari Baghbamidi, Sakineh; Beitollahi, Hadi; Karimi-Maleh, Hassan; Soltani-Nejad, Somayeh; Soltani-Nejad, Vahhab; Roodsaz, Sara

2012-01-01

A simple and convenient method is described for voltammetric determination of carbidopa (CD), based on its electrochemical oxidation at a modified multiwall carbon nanotube paste electrode. Under optimized conditions, the proposed method exhibited acceptable analytical performances in terms of linearity (over the concentration range from 0.1 to 700.0 μM), detection limit (65.0 nM), and reproducibility (RSD = 2.5%) for a solution containing CD. Also, square wave voltammetry (SWV) was used for simultaneous determination of CD, folic acid (FA), and tryptophan (TRP) at the modified electrode. To further validate its possible application, the method was used for the quantification of CD, FA, and TRP in urine samples. PMID:22666634

Hg(2+) detection using a disposable and miniaturized screen-printed electrode modified with nanocomposite carbon black and gold nanoparticles.

PubMed

Cinti, Stefano; Santella, Francesco; Moscone, Danila; Arduini, Fabiana

2016-05-01

A miniaturized screen-printed electrode (SPE) modified with a carbon black-gold nanoparticle (CBNP-AuNP) nanocomposite has been developed as an electrochemical sensor for the detection of inorganic mercury ions (Hg(2+)). The working electrode surface has been modified with nanocomposite constituted of CBNPs and AuNPs by an easy drop casting procedure that makes this approach extendible to an automatable mass production of modified SPEs. Square wave anodic stripping voltammetry (SWASV) was adopted to perform Hg(2+) detection, revealing satisfactory sensitivity and detection limit, equal to 14 μA ppb(-1) cm(-2) and 3 ppb, respectively. The applicability of the CBNP-AuNP-SPE for the determination of inorganic mercury has been assessed in river water by a simple filtration and acidification of the sample as well as in soil by means of a facile acidic extraction procedure assisted by ultrasound.

An organic surface modifier to produce a high work function transparent electrode for high performance polymer solar cells.

PubMed

Choi, Hyosung; Kim, Hak-Beom; Ko, Seo-Jin; Kim, Jin Young; Heeger, Alan J

2015-02-04

Modification of an ITO electrode with small-molecule organic surface modifier, 4-chloro-benzoic acid (CBA), via a simple spin-coating method produces a high-work-function electrode with high transparency and a hydrophobic surface. As an alternative to PEDOT:PSS, CBA modification achieves efficiency enhancement up to 8.5%, which is attributed to enhanced light absorption within the active layer and smooth hole transport from the active layer to the anode. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Glucocorticoids on the Clinical and Radiographic Efficacy of Tofacitinib in Patients with Rheumatoid Arthritis: A Posthoc Analysis of Data from 6 Phase III Studies.

PubMed

Charles-Schoeman, Christina; van der Heijde, Désirée; Burmester, Gerd R; Nash, Peter; Zerbini, Cristiano A F; Connell, Carol A; Fan, Haiyun; Kwok, Kenneth; Bananis, Eustratios; Fleischmann, Roy

2018-02-01

Tofacitinib has been investigated for the treatment of rheumatoid arthritis (RA) in phase III studies in which concomitant glucocorticoids (GC) were allowed. We analyzed the effect of GC use on efficacy outcomes in patients with RA receiving tofacitinib and/or methotrexate (MTX) or conventional synthetic disease-modifying antirheumatic drugs (csDMARD) in these studies. Our posthoc analysis included data from 6 phase III studies (NCT01039688; NCT00814307; NCT00847613; NCT00853385; NCT00856544; NCT00960440). MTX-naive patients or patients with inadequate response to csDMARD or biological DMARD received tofacitinib 5 or 10 mg twice daily alone or with csDMARD, with or without concomitant GC. Patients receiving GC (≤ 10 mg/day prednisone or equivalent) before enrollment maintained a stable dose throughout. Endpoints included the American College of Rheumatology (ACR) 20/50/70 response rates, rates of Clinical Disease Activity Index (CDAI)-defined low disease activity (LDA; CDAI ≤ 10) and remission (CDAI ≤ 2.8), and changes from baseline in CDAI, 28-joint count Disease Activity Score (DAS28-4)-erythrocyte sedimentation rate (ESR), Health Assessment Questionnaire-Disability Index (HAQ-DI), pain visual analog scale (VAS), and modified total Sharp score. Of 3200 tofacitinib-treated patients, 1258 (39.3%) received tofacitinib monotherapy and 1942 (60.7%) received tofacitinib plus csDMARD; 1767 (55.2%) received concomitant GC. ACR20/50/70 response rates, rates of CDAI LDA and remission, and improvements in CDAI, DAS28-4-ESR, HAQ-DI, and pain VAS with tofacitinib were generally similar with or without GC in monotherapy and combination therapy studies. GC use did not appear to affect radiographic progression in tofacitinib-treated MTX-naive patients. MTX plus GC appeared to inhibit radiographic progression to a numerically greater degree than MTX alone. Concomitant use of GC with tofacitinib did not appear to affect clinical or radiographic efficacy. MTX plus GC showed a trend to inhibit radiographic progression to a greater degree than MTX alone.

Gas dynamics in strong centrifugal fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bogovalov, S.V.; Kislov, V.A.; Tronin, I.V.

2015-03-10

Dynamics of waves generated by scopes in gas centrifuges (GC) for isotope separation is considered. The centrifugal acceleration in the GC reaches values of the order of 106g. The centrifugal and Coriolis forces modify essentially the conventional sound waves. Three families of the waves with different polarisation and dispersion exist in these conditions. Dynamics of the flow in the model GC Iguasu is investigated numerically. Comparison of the results of the numerical modelling of the wave dynamics with the analytical predictions is performed. New phenomena of the resonances in the GC is found. The resonances occur for the waves polarizedmore » along the rotational axis having the smallest dumping due to the viscosity.« less

Electrodeposition of platinum nanoparticles in a room-temperature ionic liquid.

PubMed

Zhang, Da; Chang, Wan Cheng; Okajima, Takeyoshi; Ohsaka, Takeo

2011-12-06

The electrochemistry of the [PtCl(6)](2-)-[PtCl(4)](2-)-Pt redox system on a glassy carbon (GC) electrode in a room-temperature ionic liquid (RTIL) [i.e., N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMEBF(4))] has been examined. The two-step four-electron reduction of [PtCl(6)](2-) to Pt, i.e., reduction of [PtCl(6)](2-) to [PtCl(4)](2-) and further reduction of [PtCl(4)](2-) to Pt, occurs separately in this RTIL in contrast to the one-step four-electron reduction of [PtCl(6)](2-) to Pt in aqueous media. The cathodic and anodic peaks corresponding to the [PtCl(6)](2-)/[PtCl(4)](2-) redox couple were observed at ca. -1.1 and 0.6 V vs a Pt wire quasi-reference electrode, respectively, while those observed at -2.8 and -0.5 V were found to correspond to the [PtCl(4)](2-)/Pt redox couple. The disproportionation reaction of the two-electron reduction product of [PtCl(6)](2-) (i.e., [PtCl(4)](2-)) to [PtCl(6)](2-) and Pt metal was also found to occur significantly. The electrodeposition of Pt nanoparticles could be carried out on a GC electrode in DEMEBF(4) containing [PtCl(6)](2-) by holding the potential at -3.5 or -2.0 V. At -3.5 V, the four-electron reduction of [PtCl(6)](2-) to Pt can take place, while at -2.0 V the two-electron reduction of [PtCl(6)](2-) to [PtCl(4)](2-) occurs. The results obtained demonstrate that the electrodeposition of Pt at -3.5 V may occur via a series of reductions of [PtCl(6)](2-) to [PtCl(4)](2-) and further [PtCl(4)](2-) to Pt and at -2.0 V via a disproportionation reaction of [PtCl(4)](2-) to [PtCl(6)](2-) and Pt. Furthermore, the deposition potential of Pt nanoparticles was found to largely influence their size and morphology as well as the relative ratio of Pt(110) and Pt(100) crystalline orientation domains. The sizes of the Pt nanoparticles prepared by holding the electrode potential at -2.0 and -3.5 V are almost the same, in the range of ca. 1-2 nm. These small nanoparticles are "grown" to form bigger particles with different morphologies: In the case of the deposition at -2.0 V, the GC electrode surface is totally, relatively compactly covered with Pt particles of relatively uniform size of ca. 10-50 nm. On the other hand, in the case of the electrodeposition at -3.5 V, small particles of ca. 50-100 nm and the grown-up particles of ca. 100-200 nm cover the GC surface irregularly and coarsely. Interestingly, the Pt nanoparticles prepared by holding the potential at -2.0 and -3.5 V are relatively enriched in Pt(100) and Pt(110) facets, respectively. © 2011 American Chemical Society

Enhancement of anodic biofilm formation and current output in microbial fuel cells by composite modification of stainless steel electrodes

NASA Astrophysics Data System (ADS)

Liang, Yuxiang; Feng, Huajun; Shen, Dongsheng; Li, Na; Guo, Kun; Zhou, Yuyang; Xu, Jing; Chen, Wei; Jia, Yufeng; Huang, Bin

2017-02-01

In this paper, we first systematically investigate the current output performance of stainless steel electrodes (SS) modified by carbon coating (CC), polyaniline coating (PANI), neutral red grafting (NR), surface hydrophilization (SDBS), and heat treatment (HEAT). The maximum current density of 13.0 A m-2 is obtained on CC electrode (3.0 A m-2 of the untreated anode). Such high performance should be attributed to its large effective surface area, which is 2.3 times that of the unmodified electrode. Compared with SS electrode, about 3-fold increase in current output is achieved with PANI. Functionalization with hydrophilic group and electron medium result in the current output rising to 1.5-2 fold, through enhancing bioadhesive and electron transport rate, respectively. CC modification is the best choice of single modification for SS electrode in this study. However, this modification is not perfect because of its poor hydrophilicity. So CC electrode is modified by SDBS for further enhancing the current output to 16 A m-2. These results could provide guidance for the choice of suitable single modification on SS electrodes and a new method for the perfection of electrode performance through composite modification.

Adsorption of Paraquat Dichloride by Graphitic Carbon Nitride Synthesized from Melamine Scraps

NASA Astrophysics Data System (ADS)

Watcharenwong, A.; Kaeokan, A.; Rammaroeng, R.; Upama, P.; Kajitvichyanukul, P.

2017-07-01

In this research, graphitic carbon nitride (g-C3N4) was synthesized from useless melamine scraps. Mixture of melamine powder and urea was directly burned in the muffle furnace at 550 °C. Later as-synthesized g-C3N4 was modified with hydrochloric acid. The g-C3N4 powder was characterized by several techniques including X-ray diffraction, scanning electron microscope, and specific surface area analyser. Adsorption of the herbicide paraquat from an aqueous solution to suspended particles of g-C3N4 was investigated, taking into consideration several parameters such as initial concentration of paraquat, initial pH, and dosage of g-C3N4. The results showed that with the same amount of g-C3N4, the increase in the paraquat concentration caused the reduction in the removal efficiency and the higher the amount of g-C3N4, the less residual paraquat remained in the bulk solution. G-C3N4 showed better adsorption behaviour in the basic condition. Finally, Langmuir and Freundlich adsorption isotherms were also evaluated. Paraquat adsorption by g-C3N4 was in accordance with Langmuir more than Freundlich adsorption isotherm.

Optimization of the electrodeposition of copper on poly-1-naphthylamine for the amperometric detection of carbohydrates in HPLC.

PubMed

D'Eramo, Fabiana; Marioli, Juan M; Arévalo, Alejandro H; Sereno, Leonides E

2003-11-04

A modified electrode consisting of copper dispersed in a poly-1-naphthylamine (p-1-NAP/Cu) film on a glassy carbon electrode was used as an amperometric detector for the on-line analysis of various carbohydrates separated by high performance liquid chromatography. The results obtained with this new sensor were compared to those obtained with a modified electrode based on the same polymer but with copper ions incorporated at open circuit, as described in a previous paper. In this new modified electrode the copper microparticles were electrochemically deposited into the polymeric matrix by single potential step chronoamperometry. A nucleation and growth mechanism was proposed to explain the current transients of copper electrodeposition. The experimental results were fitted to the proposed mechanism by using a mathematical equation that considers three-dimensional growth and progressive nucleation, assuming a no overlap and no diffusion mechanism. Cyclic voltammetric experiments showed that the electrodeposited copper microparticles provided a catalytic surface suited for the oxidation of glucose and several carbohydrates. The sensitivity of the electrode was influenced by the amount of copper electrodeposited, which in turn depended on the applied overpotential used for the deposition of copper. Liquid chromatographic experiments were carried out to test the analytical performance of these electrodes for the determination of various carbohydrates.

Boronic Acid vs. Folic Acid: A Comparison of the bio-recognition performances by Impedimetric Cytosensors based on Ferrocene cored dendrimer.

PubMed

Dervisevic, Muamer; Şenel, Mehmet; Sagir, Tugba; Isik, Sevim

2017-05-15

A comparative study is reported where folic acid (FA) and boronic acid (BA) based cytosensors and their analytical performances in cancer cell detection were analyzed by using electrochemical impedance spectroscopy (EIS) method. Cytosensors were fabricated using self-assembled monolayer principle by modifying Au electrode with cysteamine (Cys) and immobilization of ferrocene cored polyamidiamine dendrimers second generation (Fc-PAMAM (G2)), after which electrodes were modified with FA and BA. Au/Fc-PAMAM(G2)/FA and Au/Fc-PAMAM(G2)/BA based cytosensors showed extremely good analytical performances in cancer cell detection with linear range of 1×10 2 to 1×10 6 cellsml -1 , detection limit of 20cellsml -1 with incubation time of 20min for FA based electrode, and for BA based electrode detection limit was 28cellsml -1 with incubation time of 10min. Next to excellent analytical performances, cytosensors showed high selectivity towards cancer cells which was demonstrated in selectivity study using human embryonic kidney 293 cells (HEK 293) as normal cells and Au/Fc-PAMAM(G2)/FA electrode showed two times better selectivity than BA modified electrode. These cytosensors are promising for future applications in cancer cell diagnosis. Copyright © 2017 Elsevier B.V. All rights reserved.

A reference electrode based on polyvinyl butyral (PVB) polymer for decentralized chemical measurements.

PubMed

Guinovart, Tomàs; Crespo, Gastón A; Rius, F Xavier; Andrade, Francisco J

2014-04-22

A new solid-state reference electrode using a polymeric membrane of polyvinyl butyral (PVB), Ag/AgCl and NaCl to be used in decentralized chemical measurements is presented. The electrode is made by drop-casting the membrane cocktail onto a glassy carbon (GC) substrate. A stable potential (less than 1 mV dec(-1)) over a wide range of concentrations for the several chemical species tested is obtained. No significant influence to changes in redox potential, light and pH are observed. The response of this novel electrode shows good correlation when compared with a conventional double-junction reference electrode. Also good long-term stability (90±33 μV/h) and a lifetime of approximately 4 months are obtained. Aspects related to the working mechanisms are discussed. Atomic Force Microscopy (AFM) studies reveal the presence of nanopores and channels on the surface, and electrochemical impedance spectroscopy (EIS) of optimized electrodes show low bulk resistances, usually in the kΩ range, suggesting that a nanoporous polymeric structure is formed in the interface with the solution. Future applications of this electrode as a disposable device for decentralized measurements are discussed. Examples of the utilization on wearable substrates (tattoos, fabrics, etc) are provided. Copyright © 2014 Elsevier B.V. All rights reserved.

Original implementation of Electrochemical Impedance Spectroscopy (EIS) in symmetric cells: Evaluation of post-mortem protocols applied to characterize electrode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

Gordon, Isabel Jiménez; Genies, Sylvie; Si Larbi, Gregory; Boulineau, Adrien; Daniel, Lise; Alias, Mélanie

2016-03-01

Understanding ageing mechanisms of Li-ion batteries is essential for further optimizations. To determine performance loss causes, post-mortem analyses are commonly applied. For each type of post-mortem test, different sample preparation protocols are adopted. However, reports on the reliability of these protocols are rare. Herein, Li-ion pouch cells with LiNi1/3Mn1/3Co1/3O2 - polyvinylidene fluoride positive electrode, graphite-carboxymethyl cellulose-styrene rubber negative electrode and LiPF6 - carbonate solvents mixture electrolyte, are opened and electrodes are recovered following a specified protocol. Negative and positive symmetric cells are assembled and their impedances are recorded. A signal analysis is applied to reconstruct the Li-ion pouch cell impedance from the symmetric cells, then comparison against the pouch cell true impedance allows the evaluation of the sample preparation protocols. The results are endorsed by Transmission Electronic Microscopy (TEM) and Gas Chromatography - Mass Spectrometry (GC-MS) analyses. Carbonate solvents used to remove the salt impacts slightly the surface properties of both electrodes. Drying electrodes under vacuum at 25 °C produces an impedance increase, particularly very marked for the positive electrode. Drying at 50 °C under vacuum or/and exposition to the anhydrous room atmosphere is very detrimental.

Electrochemically formed 3D hierarchical thin films of cobalt-manganese (Co-Mn) hexacyanoferrate hybrids for electrochemical applications

NASA Astrophysics Data System (ADS)

Alam Venugopal, Narendra Kumar; Joseph, James

2016-02-01

Here we report the feasibility of forming 3D nanostructured hexacyanoferates of Cobalt and Manganese (Co-MnHCF) on GC surface by a facile electrochemical method. This 3D architecture on glassy carbon electrode characterised systematically by voltammetry and other physical characterisation techniques like Field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and Fourier transform Infrared spectroscopy (FTIR) etc,. Electrochemical Quartz crystal microbalance (EQCM) studies helped out to calculate the total mass change during Co-MnHCF formation. Electrochemical studies reveal that the formal redox potentials of both Co and MnHCF films remained close to that of newly formed Co-MnHCF hybrid films. These 3D modified films were successfully applied for two different electrochemical applications i) For pseudocapacitor studies in KNO3 medium ii) Investigated the electrocatalytic behaviour of redox film towards water oxidation reaction in alkaline medium. Electrochemical performances of newly formed Co-MnHCF are compared with their individual transition metal (Co, Mn) hexacyanoferrates. The resulting material shows a specific capacitance of 350 F g-1 through its fast reversible redox reaction of electrochemically formed Co-MnHCF modified film. Interestingly we showed the overpotential of 450 mV (from its thermodynamic voltage 1.2 V) to attain its optimum current density of 10 mA cm-2 for O2 evolution in alkaline medium.

Recent advances in graphite powder-based electrodes.

PubMed

Bellido-Milla, Dolores; Cubillana-Aguilera, Laura Ma; El Kaoutit, Mohammed; Hernández-Artiga, Ma Purificación; Hidalgo-Hidalgo de Cisneros, José Luis; Naranjo-Rodríguez, Ignacio; Palacios-Santander, José Ma

2013-04-01

Graphite powder-based electrodes have the electrochemical performance of quasi-noble metal electrodes with intrinsic advantages related to the possibility of modification to enhance selectivity and their easily renewable surface, with no need for hazardous acids or bases for their cleaning. In contrast with commercial electrodes, for example screen-printed or sputtered-chip electrodes, graphite powder-based electrodes can also be fabricated in any laboratory with the form and characteristics desired. They are also readily modified with advanced materials, with relatively high reproducibility. All these characteristics make them a very interesting option for obtaining a large variety of electrodes to resolve different kinds of analytical problems. This review summarizes the state-of-the-art, advantages, and disadvantages of graphite powder-based electrodes in electrochemical analysis in the 21st century. It includes recent trends in carbon paste electrodes, devoting special attention to the use of emergent materials as new binders and to the development of other composite electrodes. The most recent advances in the use of graphite powder-modified sol-gel electrodes are also described. The development of sonogel-carbon electrodes and their use in electrochemical sensors and biosensors is included. These materials extend the possibilities of applications, especially for industrial technology-transfer purposes, and their development could affect not only electroanalytical green chemistry but other interesting areas also, for example catalysis and energy conversion and storage.

A novel organophosphorus hydrolase-based biosensor using mesoporous carbons and carbon black for the detection of organophosphate nerve agents.

PubMed

Lee, Joon Hwan; Park, Jae Yeon; Min, Kyoungseon; Cha, Hyung Joon; Choi, Suk Soon; Yoo, Young Je

2010-03-15

To detect organophosphate chemicals, which are used both as pesticides and as nerve agents, a novel biosensor based on organophosphorus hydrolase was developed. By using mesoporous carbon (MC) and carbon black (CB) as an anodic layer, the sensitivity of the sensor to p-nitrophenol (PNP), which is the product of the organophosphorus hydrolase reaction, was greatly improved. The MC/CB/glass carbon (GC) layer exhibited an enhanced amperometric response relative to a carbon nanotube (CNT)-modified electrode because it promoted electron transfer of enzymatically generated phenolic compounds (p-nitrophenol). The well-ordered nanopores, many edge-plane-like defective sites (EDSs), and high surface area of the MC resulted in increased sensitivity, and allowed for nanomolar-range detection of the analyte paraoxon. Thus, MCs are suitable for use in real-time biosensors. Under the optimized experimental conditions, the biosensor had a detection limit of 0.12 microM (36 ppb) and a sensitivity of 198 nA/microM for paraoxon. (c) 2009 Elsevier B.V. All rights reserved.

Surface-modified CMOS IC electrochemical sensor array targeting single chromaffin cells for highly parallel amperometry measurements.

PubMed

Huang, Meng; Delacruz, Joannalyn B; Ruelas, John C; Rathore, Shailendra S; Lindau, Manfred

2018-01-01

Amperometry is a powerful method to record quantal release events from chromaffin cells and is widely used to assess how specific drugs modify quantal size, kinetics of release, and early fusion pore properties. Surface-modified CMOS-based electrochemical sensor arrays allow simultaneous recordings from multiple cells. A reliable, low-cost technique is presented here for efficient targeting of single cells specifically to the electrode sites. An SU-8 microwell structure is patterned on the chip surface to provide insulation for the circuitry as well as cell trapping at the electrode sites. A shifted electrode design is also incorporated to increase the flexibility of the dimension and shape of the microwells. The sensitivity of the electrodes is validated by a dopamine injection experiment. Microwells with dimensions slightly larger than the cells to be trapped ensure excellent single-cell targeting efficiency, increasing the reliability and efficiency for on-chip single-cell amperometry measurements. The surface-modified device was validated with parallel recordings of live chromaffin cells trapped in the microwells. Rapid amperometric spikes with no diffusional broadening were observed, indicating that the trapped and recorded cells were in very close contact with the electrodes. The live cell recording confirms in a single experiment that spike parameters vary significantly from cell to cell but the large number of cells recorded simultaneously provides the statistical significance.

A simple gold plate electrode modified with Gd-doped TiO₂ nanoparticles used for determination of trace nitrite in cured food.

PubMed

Zhang, M-L; Cao, Z; He, J-L; Xue, L; Zhou, Y; Long, S; Deng, T; Zhang, L

2012-01-01

A simple gold plate electrode (GPE) based on a gadolinium-doped titanium dioxide (Gd/TiO₂) ultrathin film was successfully constructed by using a surface sol-gel technique, and used for the detection of trace amounts of nitrite in cured foods. The Gd/TiO₂ nanoparticles were synthesised and characterised via scanning electron microscopy (SEM) and X-ray diffraction (XRD), indicating that the Gd-doped TiO₂ formed an anatase phase through roasting at 450°C, generating actively interstitial oxygen at the interface of the surface of TiO₂ lattice surrounded by Gd³⁺. The electro-catalytic effect for oxidation of nitrite on the modified electrode was investigated by cyclic voltammetry in 0.10 mol l⁻¹ sulfuric acid media solution, showing that the modified electrode exhibited excellent response performance to nitrite with good reproducibility, selectivity and stability. The catalytic peak current was found to be linear with nitrite concentrations in the range of 8.0 × 10⁻⁷ to 4.0 × 10⁻⁴) mol l⁻¹, with a detection limit of 5.0 × 10⁻⁷ mol l⁻¹ (S/N = 3). The modified electrode could be used for the determination of nitrite in the cured sausage samples with a satisfactory recovery in the range of 95.5-104%, showing its promising application for food safety monitoring.

Simultaneous voltammetry detection of dopamine and uric acid in human serum and urine with a poly(procaterol hydrochloride) modified glassy carbon electrode.

PubMed

Kong, Dexian; Zhuang, Qizhao; Han, Yejian; Xu, Lanping; Wang, Zeming; Jiang, Lili; Su, Jinwei; Lu, Chun-Hua; Chi, Yuwu

2018-08-01

In the present study, procaterol hydrochloride (ProH) was successfully electropolymerized onto a glass carbon electrode (GCE) with simply cyclic voltammetry scans to construct a poly(procaterol hydrochloride) (p-ProH) membrane modified electrode. Compared with the bare GCE, much higher oxidation peak current responses and better peak potentials separation could be obtained for the simultaneous oxidation of dopamine (DA) and uric acid (UA), owning to the excellent electrocatalytic ability of the p-ProH membrane. And it's based on that a square wave voltammetry (SWV) method was developed to selective and simultaneous measurement of DA and UA. Under the optimum conditions, the linear dependence of oxidation peak current on analyte concentrations were found to be 1.0-100 μmol/L and 2-100 μmol/L, giving detection limits of 0.3 μmol/L and 0.5 μmol/L for DA and UA, separately. The as prepared modified electrode shows simplicity in construction with the merits of good reproducibility, high stability, passable selectivity and nice sensitivity. Finally, the proposed p-ProH membrane modified electrode was successfully devoted to the detection of DA and UA in biological fluids such as human serum and urine with acceptable results. Copyright © 2018 Elsevier B.V. All rights reserved.

Intrapulpal Thermal Changes during Setting Reaction of Glass Carbomer® Using Thermocure Lamp.

PubMed

Kahvecioglu, Firdevs; Tosun, Gül; Ülker, Hayriye Esra

2016-01-01

Objectives . To measure the temperature increase induced during thermocure lamp setting reaction of glass carbomer and to compare it with those induced by visible light curing of a resin-modified glass ionomer and a polyacid-modified composite resin in primary and permanent teeth. Materials and Methods . Nonretentive class I cavities were prepared in extracted primary and permanent molars. Glass carbomer (GC) was placed in the cavity and set at 60°C for 60 sn using a special thermocure lamp. Resin-modified glass ionomer (RMGIC) and polyacid-modified composite resin (PMCR) were placed in the cavities and polymerized with an LED curing unit. Temperature increases during setting reactions were measured with a J-type thermocouple wire connected to a data logger. Data were examined using two-way analysis of variance and Tukey's honestly significant difference tests. Results . The use of GC resulted in temperature changes of 5.17 ± 0.92°C and 5.32 ± 0.90°C in primary and permanent teeth, respectively ( p > 0.05). Temperature increases were greatest in the GC group, differing significantly from those in the PMCR group ( p < 0.05). Conclusion . Temperature increases during polymerization and setting reactions of the materials were below the critical value in all groups. No difference was observed between primary and permanent teeth, regardless of the material used.

Biosensor Based on Self-Assembling Acetylcholinesterase on Carbon Nanotubes for Flow injection/Amperometric Detection of Organophosphate Pesticides and Nerve Agents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Guodong; Lin, Yuehe

A highly sensitive flow-injection amperometric biosensor for organophosphate pesticides and nerve agents based on self-assembly of acetylcholinesterase (AChE) on carbon nanotube (CNT)-modified glassy carbon (GC) electrode is described. AChE is immobilized on the negatively-charged CNT surface by alternatively assembling a cationic polydiallyldimethylammonium chloride (PDDA) layer and an AChE layer. Transmission electron microscopy images confirm the formation of layer-by-layer nanostructures on carboxyl functionalized CNTs. The unique sandwich-like structure (PDDA/AChE/PDDA) on the CNT surface formed by self-assembly provides a favorable microenvironment to keep the bioactivity of AChE and to prevent enzyme molecule leakage. The electrocatalytic activity of CNT leads to a greatlymore » improved electrochemical detection of the enzymatically generated thiocholine product, including a low oxidation overvoltage (+150 mV), higher sensitivity, and stability. The developed PDDA/AChE/PDDA/CNT/GC biosensor integrated into a flow injection system was used to monitor organophosphate pesticides and nerve agents, such as paraoxon. The sensor performance, including inhibition time and regeneration conditions, was optimized with respect to operating conditions. Under the optimal conditions, the biosensor was used to measure as low as 0.4 pM paraoxon with a 6-min inhibition time. The biosensor had excellent operational lifetime stability with no decrease in the activity of enzymes for more than 20 repeated measurements over a 1-week period. The developed biosensor system is an ideal tool for online monitoring of organophosphate pesticides and nerve agents.« less

Anti-tumor response induced by immunologically modified carbon nanotubes and laser irradiation using rat mammary tumor model

NASA Astrophysics Data System (ADS)

Acquaviva, Joseph T.; Hasanjee, Aamr M.; Bahavar, Cody F.; Zhou, Fefian; Liu, Hong; Howard, Eric W.; Bullen, Liz C.; Silvy, Ricardo P.; Chen, Wei R.

2015-03-01

Laser immunotherapy (LIT) is being developed as a treatment modality for metastatic cancer which can destroy primary tumors and induce effective systemic anti-tumor responses by using a targeted treatment approach in conjunction with the use of a novel immunoadjuvant, glycated chitosan (GC). In this study, Non-invasive Laser Immunotherapy (NLIT) was used as the primary treatment mode. We incorporated single-walled carbon nanotubes (SWNTs) into the treatment regimen to boost the tumor-killing effect of LIT. SWNTs and GC were conjugated to create a completely novel, immunologically modified carbon nanotube (SWNT-GC). To determine the efficacy of different laser irradiation durations, 5 minutes or 10 minutes, a series of experiments were performed. Rats were inoculated with DMBA-4 cancer cells, a highly aggressive metastatic cancer cell line. Half of the treatment group of rats receiving laser irradiation for 10 minutes survived without primary or metastatic tumors. The treatment group of rats receiving laser irradiation for 5 minutes had no survivors. Thus, Laser+SWNT-GC treatment with 10 minutes of laser irradiation proved to be effective at reducing tumor size and inducing long-term anti-tumor immunity.

A Modified Gibson Assembly Method for Cloning Large DNA Fragments with High GC Contents.

PubMed

Li, Lei; Jiang, Weihong; Lu, Yinhua

2018-01-01

Gibson one-step, isothermal assembly method (Gibson assembly) can be used to efficiently assemble large DNA molecules by in vitro recombination involving a 5'-exonuclease, a DNA polymerase and a DNA ligase. In the past few years, this robust DNA assembly method has been widely applied to seamlessly construct genes, genetic pathways and even entire genomes. Here, we expand this method to clone large DNA fragments with high GC contents, such as antibiotic biosynthetic gene clusters from Streptomyces . Due to the low isothermal condition (50 °C) in the Gibson reaction system, the complementary overlaps with high GC contents are proposed to easily form mismatched linker pairings, which leads to low assembly efficiencies mainly due to vector self-ligation. So, we modified this classic method by the following two steps. First, a pair of universal terminal single-stranded DNA overhangs with high AT contents are added to the ends of the BAC vector. Second, two restriction enzyme sites are introduced into the respective sides of the designed overlaps to achieve the hierarchical assembly of large DNA molecules. The optimized Gibson assembly method facilitates fast acquisition of large DNA fragments with high GC contents from Streptomyces.

The role of electric field in enhancing separation of gas molecules (H2S, CO2, H2O) on VIB modified g-C3N4 (0 0 1)

NASA Astrophysics Data System (ADS)

Wang, Fang; Li, Penghui; Wei, Shiqian; Guo, Jiaxing; Dan, Meng; Zhou, Ying

2018-07-01

In this study, the first-principles calculations were performed to investigate the adsorption behaviors of gas molecules H2S, CO2 and H2O on Cr, Mo and W modified g-C3N4 (0 0 1) surface. The results show that H2S, CO2 and H2O are physically adsorbed on the pristine g-C3N4, while the adsorption becomes chemisorbed due to the introduction of transition metals which significantly improve the interfacial electron transfer and narrow the band gap of g-C3N4 (0 0 1). Furthermore, it is found that the adsorption behaviors can be greatly influenced by the applied electric field. The adsorption energy is generally arranged in the order of Eads(H2S) > Eads(H2O) > Eads(CO2), and W/g-C3N4 (0 0 1) exhibits the best separation capability. The study could provide a versatile approach to selectively capture and separate the mixed gases in the catalytic reactions by controlling the applied intensity of electric field.

Amperometric determination of 6-mercaptopurine on functionalized multi-wall carbon nanotubes modified electrode by liquid chromatography coupled with microdialysis and its application to pharmacokinetics in rabbit.

PubMed

Cao, Xu-Ni; Lin, Li; Zhou, Yu-Yan; Shi, Guo-Yue; Zhang, Wen; Yamamoto, Katsunobu; Jin, Li-Tong

2003-07-27

In this paper, multi-wall carbon nanotubes functionalized with carboxylic groups modified electrode (MWNT-COOH CME) was fabricated. This chemically modified electrode (CME) can be used as the working electrode in the liquid chromatography for the determination of 6-mercaptopurine (6-MP). The results indicate that the CME exhibits efficiently electrocatalytic oxidation for 6-MP with relatively high sensitivity, stability and long-life. The peak currents of 6-MP are linear to its concentrations ranging from 4.0 x 10(-7) to 1.0 x 10(-4) mol l(-1) with the calculated detection limit (S/N=3) of 2.0 x 10(-7) mol l(-1). Coupled with microdialysis, the method has been successfully applied to the pharmacokinetic study of 6-MP in rabbit blood. This method provides a fast, sensible and simple technique for the pharmacokinetic study of 6-MP in vivo.

A New Sensitive Sensor for Simultaneous Differential Pulse Voltammetric Determination of Codeine and Acetaminophen Using a Hydroquinone Derivative and Multiwall Carbon Nanotubes Carbon Paste Electrode

PubMed Central

Garazhian, Elahe; Shishehbore, M. Reza

2015-01-01

A new sensitive sensor was fabricated for simultaneous determination of codeine and acetaminophen based on 4-hydroxy-2-(triphenylphosphonio)phenolate (HTP) and multiwall carbon nanotubes paste electrode at trace levels. The sensitivity of codeine determination was deeply affected by spiking multiwall carbon nanotubes and a modifier in carbon paste. Electron transfer coefficient, α, catalytic electron rate constant, k, and the exchange current density, j 0, for oxidation of codeine at the HTP-MWCNT-CPE were calculated using cyclic voltammetry. The calibration curve was linear over the range 0.2–844.7 μM with two linear segments, and the detection limit of 0.063 μM of codeine was obtained using differential pulse voltammetry. The modified electrode was separated codeine and acetaminophen signals by differential pulse voltammetry. The modified electrode was applied for the determination of codeine and acetaminophen in biological and pharmaceutical samples with satisfactory results. PMID:25945094

Screen-Printed Electrodes Modified with “Green” Metals for Electrochemical Stripping Analysis of Toxic Elements

PubMed Central

Economou, Anastasios

2018-01-01

This work reviews the field of screen-printed electrodes (SPEs) modified with “green” metals for electrochemical stripping analysis of toxic elements. Electrochemical stripping analysis has been established as a useful trace analysis technique offering many advantages compared to competing optical techniques. Although mercury has been the preferred electrode material for stripping analysis, the toxicity of mercury and the associated legal requirements in its use and disposal have prompted research towards the development of “green” metals as alternative electrode materials. When combined with the screen-printing technology, such environment-friendly metals can lead to disposable sensors for trace metal analysis with excellent operational characteristics. This review focuses on SPEs modified with Au, Bi, Sb, and Sn for stripping analysis of toxic elements. Different modification approaches (electroplating, bulk modification, use of metal precursors, microengineering techniques) are considered and representative applications are described. A developing related field, namely biosensing based on stripping analysis of metallic nanoprobe labels, is also briefly mentioned. PMID:29596391

Screen-Printed Electrodes Modified with "Green" Metals for Electrochemical Stripping Analysis of Toxic Elements.

PubMed

Economou, Anastasios

2018-03-29

This work reviews the field of screen-printed electrodes (SPEs) modified with "green" metals for electrochemical stripping analysis of toxic elements. Electrochemical stripping analysis has been established as a useful trace analysis technique offering many advantages compared to competing optical techniques. Although mercury has been the preferred electrode material for stripping analysis, the toxicity of mercury and the associated legal requirements in its use and disposal have prompted research towards the development of "green" metals as alternative electrode materials. When combined with the screen-printing technology, such environment-friendly metals can lead to disposable sensors for trace metal analysis with excellent operational characteristics. This review focuses on SPEs modified with Au, Bi, Sb, and Sn for stripping analysis of toxic elements. Different modification approaches (electroplating, bulk modification, use of metal precursors, microengineering techniques) are considered and representative applications are described. A developing related field, namely biosensing based on stripping analysis of metallic nanoprobe labels, is also briefly mentioned.

Application of ionic liquids in electrochemical sensing systems.

PubMed

Shiddiky, Muhammad J A; Torriero, Angel A J

2011-01-15

Since 1992, when the room temperature ionic liquids (ILs) based on the 1-alkyl-3-methylimidazolium cation were reported to provide an attractive combination of an electrochemical solvent and electrolyte, ILs have been widely used in electrodeposition, electrosynthesis, electrocatalysis, electrochemical capacitor, and lithium batteries. However, it has only been in the last few years that electrochemical biosensors based on carbon ionic liquid electrodes (CILEs) and IL-modified macrodisk electrodes have been reported. However, there are still a lot of challenges in achieving IL-based sensitive, selective, and reproducible biosensors for high speed analysis of biological and environmental compounds of interest. This review discusses the principles of operation of electrochemical biosensors based on CILEs and IL/composite-modified macrodisk electrodes. Subsequently, recent developments and major strategies for enhancing sensing performance are discussed. Key challenges and opportunities of IL-based biosensors to further development and use are considered. Emphasis is given to direct electron-transfer reaction and electrocatalysis of hemeproteins and enzyme-modified composite electrodes. Copyright © 2010 Elsevier B.V. All rights reserved.

Direct electrochemistry and electrocatalysis of glucose oxidase immobilized on reduced graphene oxide and silver nanoparticles nanocomposite modified electrode.

PubMed

Palanisamy, Selvakumar; Karuppiah, Chelladurai; Chen, Shen-Ming

2014-02-01

The direct electrochemistry of glucose oxidase (GOx) was successfully realized on electrochemically reduced graphene oxide and silver nanoparticles (RGO/Ag) nanocomposite modified electrode. The fabricated nanocomposite was characterized by field emission scanning electron microscope and energy dispersive spectroscopy. The GOx immobilized nanocomposite modified electrode showed a pair of well-defined redox peaks with a formal potential (E°) of -0.422 V, indicating that the bioactivity of GOx was retained. The heterogeneous electron transfer rate constant (Ks) of GOx at the nanocomposite was calculated to be 5.27 s(-1), revealing a fast direct electron transfer of GOx. The GOx immobilized RGO/Ag nanocomposite electrode exhibited a good electrocatalytic activity toward glucose over a linear concentration range from 0.5 to 12.5 mM with a detection limit of 0.16 mM. Besides, the fabricated biosensor showed an acceptable sensitivity and selectivity for glucose. Copyright © 2013 Elsevier B.V. All rights reserved.

A voltammetric determination of caffeic acid in red wines based on the nitrogen doped carbon modified glassy carbon electrode.

PubMed

Karikalan, Natarajan; Karthik, Raj; Chen, Shen-Ming; Chen, Hsi-An

2017-04-05

We reported an electrochemical determination of caffeic acid (CA) based on the nitrogen doped carbon (NDC). The described sensor material was prepared by the flame synthesis method, which gave an excellent platform for the synthesis of carbon nanomaterials with the hetero atom dopant. The synthesized material was confirmed by various physical characterizations and it was further characterized by different electrochemical experiments. The NDC modified glassy carbon electrode (NDC/GCE) shows the superior electrocatalytic performance towards the determination of CA with the wide linear concentration range from 0.01 to 350 μM. It achieves the lowest detection limit of 0.0024 μM and the limit of quantification of 0.004 μM. The NDC/GCE-CA sensor reveals the good selectivity, stability, sensitivity and reproducibility which endorsed that the NDC is promising electrode for the determination of CA. In addition, NDC modified electrode is applied to the determination of CA in red wines and acquired good results.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Xinfang; White, Ralph E.; Huang, Kevin

With the assumption that the Fermi level (electrochemical potential of electrons) is uniform across the thickness of a mixed ionic and electronic conducting (MIEC) electrode, the charge-transport model in the electrode domain can be reduced to the modified Fick’s first law, which includes a thermodynamic factor A. A transient numerical solution of the Nernst-Planck theory was obtained for a symmetric cell with MIEC electrodes to illustrate the validity of the assumption of a uniform Fermi level. Subsequently, an impedance numerical solution based on the modified Fick’s first law is compared with that from the Nernst-Planck theory. The results show thatmore » Nernst-Planck charge-transport model is essentially the same as the modified Fick’s first law model as long as the MIEC electrodes have a predominant electronic conductivity. However, because of the invalidity of the uniform Fermi level assumption for aMIEC electrolyte with a predominant ionic conductivity, Nernst-Planck theory is needed to describe the charge transport behaviors.« less

Application of graphene-ionic liquid-chitosan composite-modified carbon molecular wire electrode for the sensitive determination of adenosine-5'-monophosphate.

PubMed

Shi, Fan; Gong, Shixing; Xu, Li; Zhu, Huanhuan; Sun, Zhenfan; Sun, Wei

2013-12-01

In this paper, a graphene (GR) ionic liquid (IL) 1-octyl-3-methylimidazolium hexafluorophosphate and chitosan composite-modified carbon molecular wire electrode (CMWE) was fabricated by a drop-casting method and further applied to the sensitive electrochemical detection of adenosine-5'-monophosphate (AMP). CMWE was prepared with diphenylacetylene (DPA) as the modifier and the binder. The properties of modified electrode were examined by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Electrochemical behaviors of AMP was carefully investigated with enhanced responses appeared, which was due to the presence of GR-IL composite on the electrode surface with excellent electrocatalytic ability. A well-defined oxidation peak of AMP appeared at 1.314 V and the electrochemical parameters were calculated by electrochemical methods. Under the selected conditions, the oxidation peak current of AMP was proportional to its concentration in the range from 0.01 μM to 80.0 μM with the detection limit as 3.42 nM (3σ) by differential pulse voltammetry. The proposed method exhibited good selectivity and was applied to the detection of vidarabine monophosphate injection samples with satisfactory results. © 2013.

An amperometric hydrogen peroxide biosensor based on Co3O4 nanoparticles and multiwalled carbon nanotube modified glassy carbon electrode

NASA Astrophysics Data System (ADS)

Kaçar, Ceren; Dalkiran, Berna; Erden, Pınar Esra; Kiliç, Esma

2014-08-01

In this work a new type of hydrogen peroxide biosensor was fabricated based on the immobilization of horseradish peroxidase (HRP) by cross-linking on a glassy carbon electrode (GCE) modified with Co3O4 nanoparticles, multiwall carbon nanotubes (MWCNTs) and gelatin. The introduction of MWCNTs and Co3O4 nanoparticles not only enhanced the surface area of the modified electrode for enzyme immobilization but also facilitated the electron transfer rate, resulting in a high sensitivity of the biosensor. The fabrication process of the sensing surface was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Amperometric detection of hydrogen peroxide was investigated by holding the modified electrode at -0.30 V (vs. Ag/AgCl). The biosensor showed optimum response within 5 s at pH 7.0. The optimized biosensor showed linear response range of 7.4 × 10-7-1.9 × 10-5 M with a detection limit of 7.4 × 10-7. The applicability of the purposed biosensor was tested by detecting hydrogen peroxide in disinfector samples. The average recovery was calculated as 100.78 ± 0.89.

A Facile Electrochemical Preparation of Reduced Graphene Oxide@Polydopamine Composite: A Novel Electrochemical Sensing Platform for Amperometric Detection of Chlorpromazine

PubMed Central

Palanisamy, Selvakumar; Thirumalraj, Balamurugan; Chen, Shen-Ming; Wang, Yi-Ting; Velusamy, Vijayalakshmi; Ramaraj, Sayee Kannan

2016-01-01

We report a novel and sensitive amperometric sensor for chlorpromazine (CPZ) based on reduced graphene oxide (RGO) and polydopamine (PDA) composite modified glassy carbon electrode. The RGO@PDA composite was prepared by electrochemical reduction of graphene oxide (GO) with PDA. The RGO@PDA composite modified electrode shows an excellent electro-oxidation behavior to CPZ when compared with other modified electrodes such as GO, RGO and GO@PDA. Amperometric i-t method was used for the determination of CPZ. Amperometry result shows that the RGO@PDA composite detects CPZ in a linear range from 0.03 to 967.6 μM. The sensor exhibits a low detection limit of 0.0018 μM with the analytical sensitivity of 3.63 ± 0.3 μAμM–1 cm–2. The RGO@PDA composite shows its high selectivity towards CPZ in the presence of potentially interfering drugs such as metronidazole, phenobarbital, chlorpheniramine maleate, pyridoxine and riboflavin. In addition, the fabricated RGO@PDA modified electrode showed an appropriate recovery towards CPZ in the pharmaceutical tablets. PMID:27650697

In vitro extracellular recording and stimulation performance of nanoporous gold-modified multi-electrode arrays.

PubMed

Kim, Yong Hee; Kim, Gook Hwa; Kim, Ah Young; Han, Young Hwan; Chung, Myung-Ae; Jung, Sang-Don

2015-12-01

Nanoporous gold (Au) structures can reduce the impedance and enhance the charge injection capability of multi-electrode arrays (MEAs) used for interfacing neuronal networks. Even though there are various nanoporous Au preparation techniques, fabrication of MEA based on low-cost electro-codeposition of Ag:Au has not been performed. In this work, we have modified a Au MEA via the electro-codeposition of Ag:Au alloy, followed by the chemical etching of Ag, and report on the in vitro extracellular recording and stimulation performance of the nanoporous Au-modified MEA. Ag:Au alloy was electro-codeposited on a bilayer lift-off resist sputter-deposition passivated Au MEA followed by chemical etching of Ag to form a porous Au structure. The porous Au structure was analyzed by scanning electron microscopy and tunneling electron microscopy and found to have an interconnected nanoporous Au structure. The impedance value of the nanoporous Au-modified MEA is 15.4 ± 0.55 kΩ at 1 kHz, accompanied by the base noise V rms of 2.4 ± 0.3 μV. The charge injection limit of the nanoporous Au-modified electrode estimated from voltage transient measurement is approximately 1 mC cm(-2), which is comparable to roughened platinum and carbon nanotube electrodes. The charge injection capability of the nanoporous Au-modified MEA was confirmed by observing stimulus-induced spikes at above 0.2 V. The nanoporous Au-modified MEA showed mechanical durability upon ultrasonic treatment for up to an hour. Electro-codeposition of Ag:Au alloy combined with chemical etching Ag is a low-cost process for fabricating nanoporous Au-modified MEA suitable for establishing the stimulus-response relationship of cultured neuronal networks.

In vitro extracellular recording and stimulation performance of nanoporous gold-modified multi-electrode arrays

NASA Astrophysics Data System (ADS)

Kim, Yong Hee; Kim, Gook Hwa; Kim, Ah Young; Han, Young Hwan; Chung, Myung-Ae; Jung, Sang-Don

2015-12-01

Objective. Nanoporous gold (Au) structures can reduce the impedance and enhance the charge injection capability of multi-electrode arrays (MEAs) used for interfacing neuronal networks. Even though there are various nanoporous Au preparation techniques, fabrication of MEA based on low-cost electro-codeposition of Ag:Au has not been performed. In this work, we have modified a Au MEA via the electro-codeposition of Ag:Au alloy, followed by the chemical etching of Ag, and report on the in vitro extracellular recording and stimulation performance of the nanoporous Au-modified MEA. Approach. Ag:Au alloy was electro-codeposited on a bilayer lift-off resist sputter-deposition passivated Au MEA followed by chemical etching of Ag to form a porous Au structure. Main results. The porous Au structure was analyzed by scanning electron microscopy and tunneling electron microscopy and found to have an interconnected nanoporous Au structure. The impedance value of the nanoporous Au-modified MEA is 15.4 ± 0.55 kΩ at 1 kHz, accompanied by the base noise V rms of 2.4 ± 0.3 μV. The charge injection limit of the nanoporous Au-modified electrode estimated from voltage transient measurement is approximately 1 mC cm-2, which is comparable to roughened platinum and carbon nanotube electrodes. The charge injection capability of the nanoporous Au-modified MEA was confirmed by observing stimulus-induced spikes at above 0.2 V. The nanoporous Au-modified MEA showed mechanical durability upon ultrasonic treatment for up to an hour. Significance. Electro-codeposition of Ag:Au alloy combined with chemical etching Ag is a low-cost process for fabricating nanoporous Au-modified MEA suitable for establishing the stimulus-response relationship of cultured neuronal networks.

A graphene-based electrochemical sensor for sensitive detection of paracetamol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Xinhuang; Wang, Jun; Wu, Hong

2010-05-15

An electrochemical sensor based on the electrocatalytic activity of functionalized graphene for sensitive detection of paracetamol is presented. The electrochemical behaviors of paracetamol on graphene-modified glassy carbon electrodes (GCEs) were investigated by cyclic voltammetry and square-wave voltammetry. The results showed that the graphene-modified electrode exhibited excellent electrocatalytic activity to paracetamol. A quasi-reversible redox process of paracetamol at the modified electrode was obtained, and the over-potential of paracetamol decreased significantly compared with that at the bare GCE. Such electrocatalytic behavior of graphene is attributed to its unique physical and chemical properties, e.g., subtle electronic characteristics, attractive π–π interaction, and strong adsorptivemore » capability. The sensor shows great promise for simple, sensitive, and quantitative detection of paracetamol.« less

Functionalization of indium-tin-oxide electrodes by laser-nanostructured gold thin films for biosensing applications

NASA Astrophysics Data System (ADS)

Grochowska, Katarzyna; Siuzdak, Katarzyna; Karczewski, Jakub; Śliwiński, Gerard

2015-12-01

The production and properties of the indium-tin-oxide (ITO) electrodes functionalized by Au nanoparticle (NP) arrays of a relatively large area formed by pulsed laser nanostructuring of thin gold films are reported and discussed. The SEM inspection of modified electrodes reveals the presence of the nearly spherical and disc-shaped particles of dimensions in the range of 40-120 nm. The NP-array geometry can be controlled by selection of the laser processing conditions. It is shown that particle size and packing density of the array are important factors which determine the electrode performance. In the case of NP-modified electrodes the peak current corresponding to the glucose direct oxidation process shows rise with increasing glucose concentration markedly higher comparing to the reference Au disc electrode. The detection limit reaches 12 μM and linear response of the sensor is observed from 0.1 to 47 mM that covers the normal physiological range of the blood sugar detection.

Recent advances in material science for developing enzyme electrodes.

PubMed

Sarma, Anil Kumar; Vatsyayan, Preety; Goswami, Pranab; Minteer, Shelley D

2009-04-15

The enzyme-modified electrode is the fundamental component of amperometric biosensors and biofuel cells. The selection of appropriate combinations of materials, such as: enzyme, electron transport mediator, binding and encapsulation materials, conductive support matrix and solid support, for construction of enzyme-modified electrodes governs the efficiency of the electrodes in terms of electron transfer kinetics, mass transport, stability, and reproducibility. This review investigates the varieties of materials that can be used for these purposes. Recent innovation in conductive electro-active polymers, functionalized polymers, biocompatible composite materials, composites of transition metal-based complexes and organometallic compounds, sol-gel and hydro-gel materials, nanomaterials, other nano-metal composites, and nano-metal oxides are reviewed and discussed here. In addition, the critical issues related to the construction of enzyme electrodes and their application for biosensor and biofuel cell applications are also highlighted in this article. Effort has been made to cover the recent literature on the advancement of materials sciences to develop enzyme electrodes and their potential applications for the construction of biosensors and biofuel cells.

Direct on-chip DNA synthesis using electrochemically modified gold electrodes as solid support

NASA Astrophysics Data System (ADS)

Levrie, Karen; Jans, Karolien; Schepers, Guy; Vos, Rita; Van Dorpe, Pol; Lagae, Liesbet; Van Hoof, Chris; Van Aerschot, Arthur; Stakenborg, Tim

2018-04-01

DNA microarrays have propelled important advancements in the field of genomic research by enabling the monitoring of thousands of genes in parallel. The throughput can be increased even further by scaling down the microarray feature size. In this respect, microelectronics-based DNA arrays are promising as they can leverage semiconductor processing techniques with lithographic resolutions. We propose a method that enables the use of metal electrodes for de novo DNA synthesis without the need for an insulating support. By electrochemically functionalizing gold electrodes, these electrodes can act as solid support for phosphoramidite-based synthesis. The proposed method relies on the electrochemical reduction of diazonium salts, enabling site-specific incorporation of hydroxyl groups onto the metal electrodes. An automated DNA synthesizer was used to couple phosphoramidite moieties directly onto the OH-modified electrodes to obtain the desired oligonucleotide sequence. Characterization was done via cyclic voltammetry and fluorescence microscopy. Our results present a valuable proof-of-concept for the integration of solid-phase DNA synthesis with microelectronics.

Nanoband array electrode as a platform for high sensitivity enzyme-based glucose biosensing.

PubMed

Falk, Magnus; Sultana, Reshma; Swann, Marcus J; Mount, Andrew R; Freeman, Neville J

2016-12-01

We describe a novel glucose biosensor based on a nanoband array electrode design, manufactured using standard semiconductor processing techniques, and bio-modified with glucose oxidase immobilized at the nanoband electrode surface. The nanoband array architecture allows for efficient diffusion of glucose and oxygen to the electrode, resulting in a thousand-fold improvement in sensitivity and wide linear range compared to a conventional electrode. The electrode constitutes a robust and manufacturable sensing platform. Copyright © 2016 Elsevier B.V. All rights reserved.

Zinc oxide inverse opal electrodes modified by glucose oxidase for electrochemical and photoelectrochemical biosensor.

PubMed

Xia, Lei; Song, Jian; Xu, Ru; Liu, Dali; Dong, Biao; Xu, Lin; Song, Hongwei

2014-09-15

The ZnO inverse opal photonic crystals (IOPCs) were synthesized by the sol-gel method using the polymethylmethacrylate (PMMA) as a template. For glucose detection, glucose oxidase (GOD) was further immobilized on the inwall and surface of the IOPCs. The biosensing properties toward glucose of the Nafion/GOD/ZnO IOPCs modified FTO electrodes were carefully studied and the results indicated that the sensitivity of ZnO IOPCs modified electrode was 18 times than reference electrode due to the large surface area and uniform porous structure of ZnO IOPCs. Moreover, photoelectrochemical detection for glucose using the electrode was realized and the sensitivity approached to 52.4 µA mM(-1) cm(-2), which was about four times to electrochemical detection (14.1 µA mM(-1) cm(-2)). It indicated that photoelectrochemical detection can highly improve the sensor performance than conventional electrochemical method. It also exhibited an excellent anti-interference property and a good stability at the same time. This work provides a promising approach for realizing excellent photoelectrochemical biosensor of similar semiconductor photoelectric material. Copyright © 2014 Elsevier B.V. All rights reserved.

Direct electrochemistry of hemoglobin on graphene and titanium dioxide nanorods composite modified electrode and its electrocatalysis.

PubMed

Sun, Wei; Guo, Yaqing; Ju, Xiaomei; Zhang, Yuanyuan; Wang, Xiuzhen; Sun, Zhenfan

2013-04-15

A biocompatible sensing platform based on graphene (GR) and titanium dioxide (TiO₂) nanorods for the immobilization of hemoglobin (Hb) was adopted in this paper. The GR-TiO₂-Hb composite-modified carbon ionic liquid electrode was constructed through a simple casting method with Nafion as the film forming material. UV-Vis and FT-IR spectra confirmed that Hb retained its native structure in the composite film. Direct electron transfer of Hb incorporated into the composite was realized with a pair of quasi-reversible redox waves appeared, indicating that the presence of GR-TiO₂ nanocomposite on the electrode surface could facilitate the electron transfer rate between the electroactive center of Hb and the substrate electrode. Hb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid in the concentration range from 0.6 to 21.0 mmol L⁻¹. These results indicated that GR-TiO₂ nanocomposite could be a friendly biocompatible interface for immobilizing biomolecules and keeping their native structure. The fabricated biosensor displayed the advantages such as high sensitivity, good reproducibility and long-term stability. Copyright © 2012 Elsevier B.V. All rights reserved.

Ferrocene-Modified Linear Poly(ethylenimine) for Enzymatic Immobilization and Electron Mediation.

PubMed

Hickey, David P

2017-01-01

Enzymatic glucose biosensors and biofuel cells make use of the electrochemical transduction between an oxidoreductase enzyme, such as glucose oxidase (GOx), and an electrode to either quantify the amount of glucose in a solution or generate electrical energy. However, many enzymes including GOx are not able to electrochemically interact with an electrode surface directly, but require an external electrochemical relay to shuttle electrons to the electrode. Ferrocene-modified linear poly(ethylenimine) (Fc-LPEI) redox polymers have been designed to simultaneously immobilize glucose oxidase (GOx) at an electrode and mediate electron transfer from their flavin adenine dinucleotide (FAD) active site to the electrode surface. Cross-linked films of Fc-LPEI create hydrogel networks that allow for rapid transport of glucose, while the covalently bound ferrocene moieties are able to facilitate rapid electron transfer due to the ability of ferrocene to exchange electrons between adjacent ferrocene residues. For these reasons, Fc-LPEI films have been widely used in the development of high current density bioanode materials. This chapter describes the synthesis of a commonly used dimethylferrocene-modified linear poly(ethylenimine), as well as the subsequent preparation and electrochemical characterization of a GOx bioanode film utilizing the synthesized polymer.

Highly sensitive and stable electrochemical sulfite biosensor incorporating a bacterial sulfite dehydrogenase.

PubMed

Kalimuthu, Palraj; Tkac, Jan; Kappler, Ulrike; Davis, Jason J; Bernhardt, Paul V

2010-09-01

This paper describes a highly sensitive electrochemical (voltammetric) determination of sulfite using a combination of Starkeya novella sulfite dehydrogenase (SDH), horse heart cytochrome c (cyt c), and a self-assembled monolayer of 11-mercaptoundecanol (MU) cast on a gold electrode. The biosensor was optimized in terms of pH and the ratio of cyt c/SDH. The electrocatalytic oxidation current of sulfite increased linearly from 1 to 6 microM at the enzyme-modified electrode with a correlation coefficient of 0.9995 and an apparent Michaelis constant (K(M,app)) of 43 microM. Using an amperometric method, the low detection limit for sulfite at the enzyme-modified electrode was 44 pM (signal-to-noise ratio = 3). The modified electrode retained a stable response for 3 days while losing only ca. 4% of its initial sensitivity during a 2 week storage period in 50 mM Tris buffer solution at 4 degrees C. The enzyme electrode was successfully used for the determination of sulfite in beer and white wine samples. The results of these electrochemical analyses agreed well with an independent spectrophotometric method using Ellman's reagent, but the detection limit was far superior using the electrochemical method.

Electrochemical impedance immunosensor based on gold nanoparticles and aryl diazonium salt functionalized gold electrodes for the detection of antibody.

PubMed

Liu, Guozhen; Liu, Jingquan; Davis, Thomas P; Gooding, J Justin

2011-04-15

Electrodes modified with passivating organic layers have been shown to, here and previously, to exhibit good Faradaic electrochemistry upon attachment of gold nanoparticles (AuNP). Due to their low background capacitances these constructs have good potential in electrochemical sensing. Herein is reported the application of these electrode constructs for impedance based immunosensing. The immunosensor was constructed by modifying a gold electrode with 4-thiophenol (4-TP) passivating layers by diazonium salt chemistry. Subsequently, the attachment of AuNP and then a biotin derivative as a model epitope to detect anti-biotin IgG were carried out. The interfacial properties of the modified electrodes were evaluated in the presence of Fe(CN)(6)(4-/3-) redox couple as a probe by cyclic voltammetry and electrochemical impedance spectroscopy. The impedance change, due to the specific immuno-interaction at the immunosensor surface was utilized to detect anti-biotin IgG. The increase in charge-transfer resistance (R(ct)) was linearly proportional to the concentration of anti-biotin IgG in the range of 5-500 ng mL(-1), with a detection limit of 5 ng mL(-1). Copyright © 2011 Elsevier B.V. All rights reserved.

The electrocatalytic reduction of nitrate in water on Pd/Sn-modified activated carbon fiber electrode.

PubMed

Wang, Ying; Qu, Jiuhui; Wu, Rongcheng; Lei, Pengju

2006-03-01

The Pd/Sn-modified activated carbon fiber (ACF) electrodes were successfully prepared by the impregnation of Pd2+ and Sn2+ ions onto ACF, and their electrocatalytic reduction capacity for nitrate ions in water was evaluated in a batch experiment. The electrode was characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) and temperature programmed reduction (TPR). The capacity for nitrate reduction depending on Sn content on the electrode and the pH of electrolyte was discussed at length. The results showed that at an applied current density of 1.11 mA cm(-2), nitrate ions in water (solution volume: 400 mL) were reduced from 110 to 3.4 mg L(-1) after 240 min with consecutive change of intermediate nitrite. Ammonium ions and nitrogen were formed as the main final products. The amount of other possible gaseous products (including NO and N2O) was trace. With the increase of Sn content on the Pd/Sn-modified ACF electrode, the activity for nitrate reduction went up to reach a maximum (at Pd/Sn = 4) and then decreased, while the selectivity to N2 was depressed. Higher pH value of electrolyte exhibited more suppression effect on the reduction of nitrite than that of nitrate. However, no significant influence on the final ammonia formation was observed. Additionally, Cu ion in water was found to cover the active sites of the electrode to make the electrode deactivated.

Ordered mesoporous carbon modified carbon ionic liquid electrode for the electrochemical detection of double-stranded DNA.

PubMed

Zhu, Zhihong; Li, Xia; Zeng, Yan; Sun, Wei

2010-06-15

In this paper the direct electrochemistry of double-stranded DNA (dsDNA) was investigated on ordered mesoporous carbon (OMC) modified carbon ionic liquid electrode (CILE). CILE was prepared by mixing graphite powder with 1-ethyl-3-methylimidazolium ethylsulphate ([EMIM]EtOSO(3)) and liquid paraffin. A stable OMC film was formed on the surface of CILE with the help of Nafion to get a modified electrode denoted as Nafion-OMC/CILE. Due to the specific characteristics of OMC and IL present on the electrode surface, the fabricated electrode showed good electrochemical performances to different electroactive molecules. The electrochemical responses of dsDNA were carefully investigated on this electrode with two irreversible oxidation peak appeared at +1.250 V and +0.921 V (vs. SCE), which was corresponding to the oxidation of adenine and guanine residues in dsDNA structure. The electrochemical behaviors of dsDNA were carefully investigated on the Nafion-OMC/CILE. Experimental results indicated that the electron transfer rate was promoted with the increase of the oxidation peak current and the decrease of the oxidation peak potential, which was due to the electrocatalytic ability of OMC on the electrode surface. Under the optimal conditions the oxidation peak current increased with dsDNA concentration in the range of 10.0-600.0 microg mL(-1) by differential pulse voltammetry (DPV) with the detection limit of 1.2 microg mL(-1) (3sigma). Copyright 2010 Elsevier B.V. All rights reserved.

Selective in situ potential-assisted SAM formation on multi electrode arrays

NASA Astrophysics Data System (ADS)

Haag, Ann-Lauriene; Toader, Violeta; Lennox, R. Bruce; Grutter, Peter

2016-11-01

The selective modification of individual components in a biosensor array is challenging. To address this challenge, we present a generalizable approach to selectively modify and characterize individual gold surfaces in an array, in an in situ manner. This is achieved by taking advantage of the potential dependent adsorption/desorption of surface-modified organic molecules. Control of the applied potential of the individual sensors in an array where each acts as a working electrode provides differential derivatization of the sensor surfaces. To demonstrate this concept, two different self-assembled monolayer (SAM)-forming electrochemically addressable ω-ferrocenyl alkanethiols (C11) are chemisorbed onto independent but spatially adjacent gold electrodes. The ferrocene alkanethiol does not chemisorb onto the surface when the applied potential is cathodic relative to the adsorption potential and the electrode remains underivatized. However, applying potentials that are modestly positive relative to the adsorption potential leads to extensive coverage within 10 min. The resulting SAM remains in a stable state while held at potentials <200 mV above the adsorption potential. In this state, the chemisorbed SAM does not significantly desorb nor do new ferrocenylalkythiols adsorb. Using three set applied potentials provides for controlled submonolayer alkylthiol marker coverage of each independent gold electrode. These three applied potentials are dependent upon the specifics of the respective adsorbate. Characterization of the ferrocene-modified electrodes via cyclic voltammetry demonstrates that each specific ferrocene marker is exclusively adsorbed to the desired target electrode.

The effect of the carbon nanotube buffer layer on the performance of a Li metal battery

NASA Astrophysics Data System (ADS)

Zhang, Ding; Zhou, Yi; Liu, Changhong; Fan, Shoushan

2016-05-01

Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery.Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00465b

Ag electrode modified with polyhexamethylene biguanide stabilized silver nanoparticles: a new type of SERS substrates for detection of enzymatically generated thiocholine

NASA Astrophysics Data System (ADS)

Tepanov, A. A.; Nechaeva, N. L.; Prokopkina, T. A.; Kudrinskiy, A. A.; Kurochkin, I. N.; Lisichkin, G. V.

2015-11-01

The detection of thiocholine is one of the most widespread techniques for estimation of the cholinesterase activity - acetylcholinesterase and butyrylcholinesterase. Both cholinesterases can be inhibited by organophosphates and carbamates and accordingly can be considered for estimation of these pollutants in the environment. In the current work, SERS spectroscopy was applied for the thiocholine detection. The Ag electrodes modified with silver nanoparticles stabilized by polyhexamethylene biguanide were for the first time suggested as SERS-substrates for that purpose. Such electrodes can be applicable for SERS detection of submicromolar concentrations of thiocholine.

How high level of anxiety in Panic Disorder can interfere in working memory? A computer simulation and electrophysiological investigation.

PubMed

Di Giorgio Silva, Luiza Wanick; Aprigio, Danielle; Di Giacomo, Jesse; Gongora, Mariana; Budde, Henning; Bittencourt, Juliana; Cagy, Mauricio; Teixeira, Silmar; Ribeiro, Pedro; de Carvalho, Marcele Regine; Freire, Rafael; Nardi, Antonio Egidio; Basile, Luis Fernando; Velasques, Bruna

2017-12-01

Panic disorder (PD) is characterized by repeated and unexpected attacks of intense anxiety, which are not restricted to a determined situation or circumstance. The coherence function has been used to investigate the communication among brain structures through the quantitative EEG (qEEG). The objective of this study is to analyze if there is a difference in frontoparietal gamma coherence (GC) between panic disorder patients (PDP) and healthy controls (HC) during the Visual oddball paradigm; and verify if high levels of anxiety (produced by a computer simulation) affect PDP's working memory. Nine PDP (9 female with average age of 48.8, SD: 11.16) and ten HC (1 male and 9 female with average age of 38.2, SD: 13.69) were enrolled in this study. The subjects performed the visual oddball paradigm simultaneously to the EEG record before and after the presentation of computer simulation (CS). A two-way ANOVA was applied to analyze the factors Group and the Moment for each pair of electrodes separately, and another one to analyze the reaction time variable. We verified a F3-P3 GC increased after the CS movie, demonstrating the left hemisphere participation during the anxiety processing. The greater GC in HC observed in the frontal and parietal areas (P3-Pz, F4-F8 and Fp2-F4) points to the participation of these areas with the expected behavior. The greater GC in PDP for F7-F3 and F4-P4 pairs of electrodes assumes that it produces a prejudicial "noise" during information processing, and can be associated to interference on the communication between frontal and parietal areas. This "noise" during information processing is related to PD symptoms, which should be better known in order to develop effective treatment strategies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Porous carbon derived from aniline-modified fungus for symmetrical supercapacitor electrodes

DOE PAGES

Wang, Keliang; Xu, Ming; Wang, Xiaomin; ...

2017-01-23

N incorporated carbon materials are proven to be efficient EDLCs electrode materials. In this work, aniline modified fungus served as a raw material, and N-doped porous activated carbon is prepared via an efficient KOH activation method. A porous network with a high specific surface area of 2339 m 2g -1 is displayed by the prepared carbon material, resulting in a high accessible surface area and low ion diffusion resistance which is desirable for EDLC electrode materials. In assembled EDLCs, the N–AC based electrode exhibits a specific capacitance of 218 F g -1 at a current density of 0.1 A gmore » -1. Besides, excellent stability is displayed after 5000 continuous cycles at different current densities ranging from 0.1 to 10 A g -1. Thus, the present work reveals a promising candidate for electrode materials of EDLCs.« less

A novel mutation MT-COIII m.9267G>C and MT-COI m.5913G>A mutation in mitochondrial genes in a Tunisian family with maternally inherited diabetes and deafness (MIDD) associated with sever nephropathy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tabebi, Mouna, E-mail: mouna.biologiste@yahoo.com; Mkaouar-Rebai, Emna; Mnif, Mouna

Mitochondrial diabetes (MD) is a heterogeneous disorder characterized by a chronic hyperglycemia, maternal transmission and its association with a bilateral hearing impairment. Several studies reported mutations in mitochondrial genes as potentially pathogenic for diabetes, since mitochondrial oxidative phosphorylation plays an important role in glucose-stimulated insulin secretion from beta cells. In the present report, we studied a Tunisian family with mitochondrial diabetes (MD) and deafness associated with nephropathy. The mutational analysis screening revealed the presence of a novel heteroplasmic mutation m.9276G>C in the mitochondrial COIII gene, detected in mtDNA extracted from leukocytes of a mother and her two daughters indicating thatmore » this mutation is maternally transmitted and suggest its implication in the observed phenotype. Bioinformatic tools showed that m.9267G>C mutation (p.A21P) is « deleterious » and it can modify the function and the stability of the MT-COIII protein by affecting the assembly of mitochondrial COX subunits and the translocation of protons then reducing the activity of the respective OXPHOS complexes of ATP synthesis. The nonsynonymous mutation (p.A21P) has not been reported before, it is the first mutation described in the COXIII gene which is related to insulin dependent mitochondrial diabetes and deafness and could be specific to the Tunisian population. The m.9267G>C mutation was present with a nonsynonymous inherited mitochondrial homoplasmic variation MT-COI m.5913 G>A (D4N) responsible of high blood pressure, a clinical feature detected in all explored patients. - Highlights: • MT-COX3 m.9267G>C (p.A21P), heteroplasmic substitution, is not reported in any database. • m.9267G>C can be responsible of the MIDD associated with nephropaty. • This substitution can modify the function and the stability of the MT-CO3 protein. • This substitution can modify MT-CO3 structure (2D and 3D). • MT-COX3 m.9267G>C is associated with MT-CO1 m.5913G>A a homoplasmic substitution.« less

Polyaniline-Modified Oriented Graphene Hydrogel Film as the Free-Standing Electrode for Flexible Solid-State Supercapacitors.

PubMed

Du, Pengcheng; Liu, Huckleberry C; Yi, Chao; Wang, Kai; Gong, Xiong

2015-11-04

In this study, we report polyaniline (PANI)-modified oriented graphene hydrogel (OGH) films as the free-standing electrode for flexible solid-state supercapacitors (SCs). The OGH films are prepared by a facile filtration method using chemically converted graphene sheets and then introduced to PANI on the surface of OGH films by in situ chemical polymerization. The PANI-modified OGH films possess high flexibility, high electrical conductivity, and mechanical robustness. The flexible solid-state SCs based on the PANI-modified OGH films exhibit a specific capacitance of 530 F/g, keeping 80% of its original value up to 10 000 charge-discharge cycles at the current density of 10 A/g. Remarkably, the flexible solid-state SCs maintain ∼100% capacitance retention bent at 180° for 250 cycles. Moreover, the flexible solid-state SCs are further demonstrated to be able to light up a red-light-emitting diode. These results indicate that the flexible solid-state SCs based on PANI-modified OGH films as the free-standing electrode have potential applications as energy-storage devices.

Spontaneous modification of graphite anode by anthraquinone-2-sulfonic acid for microbial fuel cells.

PubMed

Tang, Xinhua; Li, Haoran; Du, Zhuwei; Ng, How Yong

2014-07-01

In this study, anthraquinone-2-sulfonic acid (AQS), an electron transfer mediator, was immobilized onto graphite felt surface via spontaneous reduction of the in situ generated AQS diazonium cations. Cyclic voltammetry (CV) and energy dispersive spectrometry (EDS) characterizations of AQS modified graphite demonstrated that AQS was covalently grafted onto the graphite surface. The modified graphite, with a surface AQS concentration of 5.37 ± 1.15 × 10(-9)mol/cm(2), exhibited good electrochemical activity and high stability. The midpoint potential of the modified graphite was about -0.248 V (vs. normal hydrogen electrode, NHE), indicating that electrons could be easily transferred from NADH in bacteria to the electrode. AQS modified anode in MFCs increased the maximum power density from 967 ± 33 mW/m(2) to 1872 ± 42 mW/m(2). These results demonstrated that covalently modified AQS functioned as an electron transfer mediator to facilitate extracellular electron transfer from bacteria to electrode and significantly enhanced the power production in MFCs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Spray-on electrodes enable EKG monitoring of physically active subjects

NASA Technical Reports Server (NTRS)

1966-01-01

Easily applied EKG electrodes monitor the heart signals of human subjects engaged in various physical exercises. The electrodes are formed from an air drying, electrically conductive cement mixture that can be applied to the skin by means of a modified commercially available spray gun.

Electrodes from carbon nanotubes/NiO nanocomposites synthesized in modified Watts bath for supercapacitors

NASA Astrophysics Data System (ADS)

Hakamada, Masataka; Abe, Tatsuhiko; Mabuchi, Mamoru

2016-09-01

A modified Watts bath coupled with pulsed current electroplating is used to uniformly deposit ultrafine nickel oxide particles (diameter < 4 nm) on multiwalled carbon nanotubes. The capacitance of the multiwalled carbon nanotubes/nickel oxide electrodes was as high as 2480 F g-1 (per mass of nickel oxide), which is close to the theoretical capacitance of NiO.

Fabrication of Metal Nanoparticle-Modified Screen Printed Carbon Electrodes for the Evaluation of Hydrogen Peroxide Content in Teeth Whitening Strips

ERIC Educational Resources Information Center

Popa, Adriana; Abenojar, Eric C.; Vianna, Adam; Buenviaje, Czarina Y. A.; Yang, Jiahua; Pascual, Cherrie B.; Samia, Anna Cristina S.

2015-01-01

A laboratory experiment in which students synthesize Ag, Au, and Pt nanoparticles (NPs) and use them to modify screen printed carbon electrodes for the electroanalysis of the hydrogen peroxide content in commercially available teeth whitening strips is described. This experiment is designed for two 3-h laboratory periods and can be adapted for…

Biotic and abiotic characterization of bioanodes formed on oxidized carbon electrodes as a basis to predict their performance.

PubMed

Cercado, Bibiana; Cházaro-Ruiz, Luis Felipe; Ruiz, Vianey; López-Prieto, Israel de Jesús; Buitrón, Germán; Razo-Flores, Elías

2013-12-15

Bioelectrochemical systems (BESs) are based on the catalytic activity of biofilm on electrodes, or the so-called bioelectrodes, to produce electricity and other valuable products. In order to increase bioanode performance, diverse electrode materials and modification methods have been implemented; however, the factors directly affecting performance are yet unclear. In this work carbon cloth electrodes were modified by thermal, chemical, and electrochemical oxidation to enhance oxygenated surface groups, to modify the electrode texture, and consequently the electron transfer rate and biofilm adhesion. The oxidized electrodes were physically, chemically, and electrochemically characterized, then bioanodes were formed at +0.1 V vs. Ag/AgCl using domestic wastewater amended with acetate. The bioanode performance was evaluated according to the current and charge generated. The efficacy of the treatments were in the order Thermal>Electrochemical>Untreated>Chemical oxidation. The maximum current observed with untreated electrode was 0.152±0.026 mA (380±92 mA m(-2)), and it was increased by 78% and 28% with thermal and electrochemical oxidized electrodes, respectively. Moreover, the volatile solids correlated significantly with the maximum current obtained, and the electrode texture was revealed as a critical factor for increasing the bioanode performance. Copyright © 2013 Elsevier B.V. All rights reserved.

Analytical design of modified Smith predictor for unstable second-order processes with time delay

NASA Astrophysics Data System (ADS)

Ajmeri, Moina; Ali, Ahmad

2017-06-01

In this paper, a modified Smith predictor using three controllers, namely, stabilising (Gc), set-point tracking (Gc1), and load disturbance rejection (Gc2) controllers is proposed for second-order unstable processes with time delay. Controllers of the proposed structure are tuned using direct synthesis approach as this method enables the user to achieve a trade-off between the performance and robustness by adjusting a single design parameter. Furthermore, suitable values of the tuning parameters are recommended after studying their effect on the closed-loop performance and robustness. This is the main advantage of the proposed work over other recently published manuscripts, where authors provide only suitable ranges for the tuning parameters in spite of giving their suitable values. Simulation studies show that the proposed method results in satisfactory performance and improved robustness as compared to the recently reported control schemes. It is observed that the proposed scheme is able to work in the noisy environment also.

Microwave modification of surface hydroxyl density for g-C3N4 with enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

An, Na; Zhao, Yang; Mao, Zhiyong; Agrawal, Dinesh Kumar; Wang, Dajian

2018-03-01

Microwave modification was performed on graphitic carbon nitride (g-C3N4) photocatalysts to tail the surface hydroxyl content for enhanced photocatalytic activity in this work. The influence of microwave heating on the surface hydroxyl density was investigated by a suite of characterization methods. The microwave treated g-C3N4 (MT-g-C3N4) delivered a higher photocatalytic activity in degradation of Rhodamine B (RhB) under visible light irradiation than pristine g-C3N4 due to its improved separation efficiency of photogenerated charge carries and promoted absorption capacity of RhB reactants on surface, which resulted from the increased surface hydroxyl density induced by microwave treatment. This study provides a simple and convenient method to modify g-C3N4 materials with enhanced photocatalytic activity for the potential application in photocatalytic elimination of environmental pollutants.

Novel Sulfur Host Composed of Cobalt and Porous Graphitic Carbon Derived from MOFs for the High-Performance Li-S Battery.

PubMed

Lu, Yan-Qiu; Wu, Yi-Jin; Sheng, Tian; Peng, Xin-Xing; Gao, Zhen-Guang; Zhang, Shao-Jian; Deng, Li; Nie, Rui; Światowska, Jolanta; Li, Jun-Tao; Zhou, Yao; Huang, Ling; Zhou, Xiao-Dong; Sun, Shi-Gang

2018-04-25

A composite consisting of cobalt and graphitic porous carbon (Co@GC-PC) is synthesized from bimetallic metal-organic frameworks and employed as the sulfur host for high-performance Li-S batteries. Because of the presence of a large surface area (724 m 2 g -1 ) and an abundance of macro-/mesopores, the Co@GC-PC electrode is able to alleviate the debilitating effect originating from the volume expansion/contraction of sulfur species during the cycling process. Our in situ UV/vis analysis indicates that the existence of Co@GC-PC promotes the adsorption of polysulfides during the discharge process. Density functional theory calculations show a strong interaction between Co and Li 2 S and a low decomposition barrier of Li 2 S on Co(111), which is beneficial to the following Li 2 S oxidation in the charge process. As a result, at 0.2C, the discharge capacity of the S/Co@GC-PC cathode is stabilized at 790 mAh g -1 after 220 cycles, much higher than that of a carbon-based cathode, which delivers a discharge capacity of 188 mAh g -1 .

Bioelectrochemistry of heme peptide at seamless three-dimensional carbon nanotubes/graphene hybrid films for highly sensitive electrochemical biosensing.

PubMed

Komori, Kikuo; Terse-Thakoor, Trupti; Mulchandani, Ashok

2015-02-18

A seamless three-dimensional hybrid film consisting of carbon nanotubes grown at the graphene surface (CNTs/G) is a promising material for the application to highly sensitive enzyme-based electrochemical biosensors. The CNTs/G film was used as a conductive nanoscaffold for enzymes. The heme peptide (HP) was immobilized on the surface of the CNTs/G film for amperometric sensing of H2O2. Compared with flat graphene electrodes modified with HP, the catalytic current for H2O2 reduction at the HP-modified CNTs/G electrode increased due to the increase in the surface coverage of HP. In addition, microvoids in the CNTs/G film contributed to diffusion of H2O2 to modified HP, resulting in the enhancement of the catalytic cathodic currents. The kinetics of the direct electron transfer from the CNTs/G electrode to compound I and II of modified HP was also analyzed.

Au-TiO2/Chit modified sensor for electrochemical detection of trace organophosphates insecticides.

PubMed

Qu, Yunhe; Min, Hong; Wei, Yinyin; Xiao, Fei; Shi, Guoyue; Li, Xiaohua; Jin, Litong

2008-08-15

In this paper, Au-TiO2/Chit modified electrode was prepared with Au-TiO2 nanocomposite (Au-TiO2) and Chitosan (Chit) as a conjunct. The Au-TiO2 nanocomposite and the films were characterized by electrochemical and spectroscopy methods. A set of experimental conditions was also optimized for the film's fabrication. The electrochemical and electrocatalytic behaviors of Au-TiO2/Chit modified electrode to trace organophosphates (OPs) insecticides such as parathion were discussed in this work. By differential pulse voltammetry (DPV) measurement, the current responses of Au-TiO2/Chit modified electrode were linear with parathion concentration ranging from 1.0 ng/ml to 7.0 x 10(3)ng/ml with the detection limit of 0.5 ng/ml. In order to evaluate the performance of the detection system, we also examined the real samples successfully in this work. It exhibited a sensitive, rapid and easy-to-use method for the fast determination of trace OPs insecticides.

A 3D Microfluidic Chip for Electrochemical Detection of Hydrolysed Nucleic Bases by a Modified Glassy Carbon Electrode

PubMed Central

Vlachova, Jana; Tmejova, Katerina; Kopel, Pavel; Korabik, Maria; Zitka, Jan; Hynek, David; Kynicky, Jindrich; Adam, Vojtech; Kizek, Rene

2015-01-01

Modification of carbon materials, especially graphene-based materials, has wide applications in electrochemical detection such as electrochemical lab-on-chip devices. A glassy carbon electrode (GCE) modified with chemically alternated graphene oxide was used as a working electrode (glassy carbon modified by graphene oxide with sulphur containing compounds and Nafion) for detection of nucleobases in hydrolysed samples (HCl pH = 2.9, 100 °C, 1 h, neutralization by NaOH). It was found out that modification, especially with trithiocyanuric acid, increased the sensitivity of detection in comparison with pure GCE. All processes were finally implemented in a microfluidic chip formed with a 3D printer by fused deposition modelling technology. As a material for chip fabrication, acrylonitrile butadiene styrene was chosen because of its mechanical and chemical stability. The chip contained the one chamber for the hydrolysis of the nucleic acid and another for the electrochemical detection by the modified GCE. This chamber was fabricated to allow for replacement of the GCE. PMID:25621613

A 3D microfluidic chip for electrochemical detection of hydrolysed nucleic bases by a modified glassy carbon electrode.

PubMed

Vlachova, Jana; Tmejova, Katerina; Kopel, Pavel; Korabik, Maria; Zitka, Jan; Hynek, David; Kynicky, Jindrich; Adam, Vojtech; Kizek, Rene

2015-01-22

Modification of carbon materials, especially graphene-based materials, has wide applications in electrochemical detection such as electrochemical lab-on-chip devices. A glassy carbon electrode (GCE) modified with chemically alternated graphene oxide was used as a working electrode (glassy carbon modified by graphene oxide with sulphur containing compounds and Nafion) for detection of nucleobases in hydrolysed samples (HCl pH = 2.9, 100 °C, 1 h, neutralization by NaOH). It was found out that modification, especially with trithiocyanuric acid, increased the sensitivity of detection in comparison with pure GCE. All processes were finally implemented in a microfluidic chip formed with a 3D printer by fused deposition modelling technology. As a material for chip fabrication, acrylonitrile butadiene styrene was chosen because of its mechanical and chemical stability. The chip contained the one chamber for the hydrolysis of the nucleic acid and another for the electrochemical detection by the modified GCE. This chamber was fabricated to allow for replacement of the GCE.

Voltammetric studies of Azathioprine on the surface of graphite electrode modified with graphene nanosheets decorated with Ag nanoparticles.

PubMed

Asadian, Elham; Iraji Zad, Azam; Shahrokhian, Saeed

2016-01-01

By using graphene nanosheets decorated with Ag nanoparticles (AgNPs-G) as an effective approach for the surface modification of pyrolytic graphite electrode (PGE), a sensing platform was fabricated for the sensitive voltammetric determination of Azathioprine (Aza). The prepared AgNPs-G nanosheets were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-vis and Raman spectroscopy techniques. The electrochemical behavior of Aza was investigated by means of cyclic voltammetry. Comparing to the bare PGE, a remarkable enhancement was observed in the response characteristics of Aza on the surface of the modified electrode (AgNPs-G/PGE) as well as a noticeable decrease in its reduction overpotential. These results can be attributed to the incredible enlargement in the microscopic surface area of the electrode due to the presence of graphene nanosheets together with strong adsorption of Aza on its surface. The effect of experimental parameters such as accumulation time, the amount of modifier suspension and pH of the supporting electrolyte were also optimized toward obtaining the maximum sensitivity. Under the optimum conditions, the calibration curve studies demonstrated that the peak current increased linearly with Aza concentrations in the range of 7 × 10(-7) to 1 × 10(-4)mol L(-1) with the detection limit of 68 nM. Further experiments revealed that the modified electrode can be successfully applied for the accurate determination of Aza in pharmaceutical preparations. Copyright © 2015 Elsevier B.V. All rights reserved.

Highly selective determination of dopamine in the presence of ascorbic acid and serotonin at glassy carbon electrodes modified with carbon nanotubes dispersed in polyethylenimine.

PubMed

Rodríguez, Marcela C; Rubianes, María D; Rivas, Gustavo A

2008-11-01

We report the highly selective and sensitive voltammetric dopamine quantification in the presence of ascorbic acid and serotonin by using glassy carbon electrodes modified with a dispersion of multi-wall carbon nanotubes (MWCNT) in polyethylenimine, PEI (GCE/MWCNT-PEI). The electrocatalytic activity of the MWCNT deposited on the glassy carbon electrode has allowed an important decrease in the overvoltages for the oxidation of ascorbic acid and dopamine, making possible a clear definition of dopamine, serotonin and ascorbic acid oxidation processes. The sensitivities for dopamine in the presence and absence of 1.0 mM ascorbic acid and serotonin were (2.18 +/- 0.03) x 10(5) microAM(-1) (r = 0.9998); and (2.10 +/- 0.07) x 10(5) miroAM(-1) (r=0.9985), respectively, demonstrating the excellent performance of the GCE/MWCNT-PEI. The detection limit for dopamine in the mixture was 9.2 x 10(-7) M. The R. S. D. for the determination of 50 microM dopamine using four different electrodes was 3.9% when modified with the same MWCNT/PEI dispersion, and 4.6% when using four different dispersions. The modified electrode has been successfully applied for recovery assays of dopamine in human blood serum. Therefore, the new sensor represents an interesting and promising alternative for the electrochemical quantification of neurotransmitters and other analytes of clinical interest.

Causality Analysis of Neural Connectivity: Critical Examination of Existing Methods and Advances of New Methods

PubMed Central

Hu, Sanqing; Dai, Guojun; Worrell, Gregory A.; Dai, Qionghai; Liang, Hualou

2012-01-01

Granger causality (GC) is one of the most popular measures to reveal causality influence of time series and has been widely applied in economics and neuroscience. Especially, its counterpart in frequency domain, spectral GC, as well as other Granger-like causality measures have recently been applied to study causal interactions between brain areas in different frequency ranges during cognitive and perceptual tasks. In this paper, we show that: 1) GC in time domain cannot correctly determine how strongly one time series influences the other when there is directional causality between two time series, and 2) spectral GC and other Granger-like causality measures have inherent shortcomings and/or limitations because of the use of the transfer function (or its inverse matrix) and partial information of the linear regression model. On the other hand, we propose two novel causality measures (in time and frequency domains) for the linear regression model, called new causality and new spectral causality, respectively, which are more reasonable and understandable than GC or Granger-like measures. Especially, from one simple example, we point out that, in time domain, both new causality and GC adopt the concept of proportion, but they are defined on two different equations where one equation (for GC) is only part of the other (for new causality), thus the new causality is a natural extension of GC and has a sound conceptual/theoretical basis, and GC is not the desired causal influence at all. By several examples, we confirm that new causality measures have distinct advantages over GC or Granger-like measures. Finally, we conduct event-related potential causality analysis for a subject with intracranial depth electrodes undergoing evaluation for epilepsy surgery, and show that, in the frequency domain, all measures reveal significant directional event-related causality, but the result from new spectral causality is consistent with event-related time–frequency power spectrum activity. The spectral GC as well as other Granger-like measures are shown to generate misleading results. The proposed new causality measures may have wide potential applications in economics and neuroscience. PMID:21511564

Oxide modified air electrode surface for high temperature electrochemical cells

DOEpatents

Singh, Prabhakar; Ruka, Roswell J.

1992-01-01

An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

High cycle life secondary lithium battery

NASA Technical Reports Server (NTRS)

Yen, Shiao-Ping S. (Inventor); Shen, David H. (Inventor); Carter, Boyd J. (Inventor); Somoano, Robert B. (Inventor)

1985-01-01

A secondary battery (10) of high energy density and long cycle is achieved by coating the separator (18) with a film (21) of cationic polymer such as polyvinyl-imidazoline. The binder of the positive electrode (14) such as an ethylene-propylene elastomer binder (26) containing particles (28) of TiS.sub.2 chalcogenide can also be modified to contain sulfone functional groups by incorporating liquid or solid sulfone materials such as 0.1 to 5 percent by weight of sulfolane into the binder. The negative lithium electrode (14), separator (18) and positive electrode (16) are preferably spirally wound and disposed within a sealed casing (17) containing terminals (32, 34). The modified separator and positive electrode are more wettable by the electrolytes in which a salt is dissolved in a polar solvent such as sulfolane.

Peptide nanotube-modified electrodes for enzyme-biosensor applications.

PubMed

Yemini, Miri; Reches, Meital; Gazit, Ehud; Rishpon, Judith

2005-08-15

The fabrication and notably improved performance of composite electrodes based on modified self-assembled diphenylalanine peptide nanotubes is described. Peptide nanotubes were attached to gold electrodes, and we studied the resulting electrochemical behavior using cyclic voltammetry and chronoamperometry. The peptide nanotube-based electrodes demonstrated a direct and unmediated response to hydrogen peroxide and NADH at a potential of +0.4 V (vs SCE). This biosensor enables a sensitive determination of glucose by monitoring the hydrogen peroxide produced by an enzymatic reaction between the glucose oxidase attached to the peptide nanotubes and glucose. In addition, the marked electrocatalytic activity toward NADH enabled a sensitive detection of ethanol using ethanol dehydrogenase and NAD+. The peptide nanotube-based amperometric biosensor provides a potential new tool for sensitive biosensors and biomolecular diagnostics.

Electrochemical luminescence determination of hyperin using a sol-gel@graphene luminescent composite film modified electrode for solid phase microextraction

NASA Astrophysics Data System (ADS)

Zou, Xiaojun; Shang, Fang; Wang, Sui

2017-02-01

In this paper, a novel electrochemiluminescence (ECL) sensor of sol-gel@graphene luminescent composite film modified electrode for hyperin determination was prepared using graphene (G) as solid-phase microextraction (SPME) material, based on selective preconcentration of target onto an electrode and followed by luminol ECL detection. Hyperin was firstly extracted from aqueous solution through the modified GCE. Hydrogel, electrogenerated chemiluminescence reagents, pH of working solution, extraction time and temperature and scan rate were discussed. Under the optimum conditions, the change of ECL intensity was in proportion to the concentration of hyperin in the range of 0.02-0.24 μg/mL with a detection limit of 0.01 μg/mL. This method showed good performance in stability, reproducibility and precision for the determination of hyperin.

Amperometric sensing of hydrogen peroxide using glassy carbon electrode modified with copper nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sophia, J.; Muralidharan, G., E-mail: muraligru@gmail.com

2015-10-15

In this paper, fabrication of glassy carbon electrode (GCE) modified with nano copper particles is discussed. The modified electrode has been tested for the non-enzymatic electrochemical detection of hydrogen peroxide (H{sub 2}O{sub 2}). The copper nanoparticles (Cu NPs) were prepared employing a simple chemical reduction method. The presence of Cu NPs was confirmed through UV–visible (UV–vis) absorption spectroscopy and X-ray diffraction (XRD) analysis. The size and morphology of the particles were investigated using transmission electron microscopy (TEM). The electrochemical properties of the fabricated sensor were studied via cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The electrochemical sensor displayedmore » excellent performance features towards H{sub 2}O{sub 2} detection exhibiting wide linear range, low detection limit, swift response time, good reproducibility and stability.« less

An electrochemical biosensor based on nanoporous stainless steel modified by gold and palladium nanoparticles for simultaneous determination of levodopa and uric acid.

PubMed

Rezaei, Behzad; Shams-Ghahfarokhi, Leila; Havakeshian, Elaheh; Ensafi, Ali A

2016-09-01

In this paper, an electrochemical biosensor based on gold and palladium nano particles-modified nanoporous stainless steel (Au-Pd/NPSS) electrode has been introduced for the simultaneous determination of levodopa (LD) and uric acid (UA). To prepare the electrode, the stainless steel was anodized to fabricate NPSS and then Cu was electrodeposited onto the nanoporous steel by applying the multiple step potential. Finally, the electrode was immersed into a gold and palladium precursor's solution by the atomic ratio of 9:1 to form Au-Pd/NPSS through the galvanic replacement reaction. Morphological aspects, structural properties and the electroanalytical behavior of the Au-Pd/NPSS electrode were studied using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and voltammetric techniques. Also, differential pulse voltammetry (DPV) was used for the simultaneous determination of LD and UA. According to results, the surface of Au-Pd/NPSS electrode contained Au and Pd nanoparticles with an average diameter of 75nm. The electrode acted better than Au/NPSS and Pd/NPSS electrodes for the simultaneous determination of LD and UA, with the peak separation potential of about 220mV. Also, the calibration plot for LD was in two linear concentration ranges of 5.0-10.0 and 10.0-55.0μmolL(-1) and for UA, it was in the range of 100-1200μmolL(-1). The detection limit for LD and UA was 0.2 and 15μmolL(-1), respectively. The modified electrode had a good performance for LD and UA detection in urine, blood serum and levodopa C-Forte tablet. Copyright © 2016 Elsevier B.V. All rights reserved.

Investigation of DBS electro-oxidation reaction in the aqueous-organic solution of LiClO4.

PubMed

Darlewski, Witold; Popiel, Stanisław; Nalepa, Tomasz; Gromotowicz, Waldemar; Szewczyk, Rafał; Stankiewicz, Romuald

2010-03-15

A process of dibutyl sulphide (DBS) electro-oxidation using electrolysis and cyclic voltamperometry was investigated in water-methanol solution using different electrodes (platinum, boron doped diamond, graphite and glassy carbon). Obtained results indicate that the DBS electro-oxidation process is irreversible in voltamperometric conditions. It was shown that during DBS electrolytic oxidation on Pt, at the low anode potential (1.8 V), DBS was oxidized to sulphoxide and sulphone. Electrolysis at higher potential (up to 3.0 V) resulted in complete DBS oxidation and formation of various products, including: butyric acid, sulphuric acid, butanesulphinic acid, butanesulphonic acid, identified using gas chromatography (GC-AED) and mass spectrometry (GC-MS) methods. (c) 2009 Elsevier B.V. All rights reserved.

Modified properties of a glycated and cross-linked soy protein isolate by transglutaminase and an oligochitosan of 5 kDa.

PubMed

Fu, Miao; Zhao, Xin-Huai

2017-01-01

Soy protein is an important protein ingredient for the food industry; however, its properties can be improved by enzymatic and chemical modifications. This study applied a new enzymatic glycation and cross-linking to modify soy protein isolate (SPI), using an oligochitosan of 5 kDa and transglutaminase. Properties of the obtained glycated and cross-linked SPI (GC-SPI) were unknown and thus assessed. GC-SPI contained glucosamine of 13.6 g kg -1 protein, but less reactable &bond;NH 2 than SPI (0.42 vs. 0.50 mol kg -1 protein). Infrared spectra and circular dichroism results showed that GC-SPI other than SPI and cross-linked SPI had more &bond;OH in molecules, and was more disordered in secondary structure. In comparison with SPI, GC-SPI showed enhanced water-binding capacity, could form aggregates with enlarged hydrodynamic radius (180.2 vs. 82.9 nm) and negative zeta-potential (-31.2 vs. -27.7 mV) in dispersion, but exhibited lower thermal stability (e.g. greater mass loss) upon heating at a temperature above 288 °C. GC-SPI also had lower in vitro proteolytic digestibility than SPI due to the protein cross-linking. Oligochitosan of 5 kDa and transglutaminase can be used to glycate and cross-link SPI. This approach is applicable to generate potential protein ingredient with good hydration and dispersive stabilisation. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Gum chewing improves swallow frequency and latency in Parkinson patients: a preliminary study.

PubMed

South, Angela R; Somers, Stephanie M; Jog, Mandar S

2010-04-13

Reduced swallowing frequency affects secretion management in Parkinson disease (PD). Gum chewing increases saliva flow and swallow frequency. This study uses chewing gum to modify swallow frequency and latency between swallows in patients with PD. 1) Assess the frequency and latency of swallow at baseline (BL), during gum chewing (GC), and post gum chewing (PGC) for participants with PD (stage 2-4) nonsymptomatic for prandial dysphagia; and 2) assess carryover after gum is expectorated. Twenty participants were studied across 3 tasks, each of 5 minutes in duration: BL, GC, and PGC. Respiratory and laryngeal signals were continuously recorded using PowerLab (version 5.5.5; ADI Instruments, Castle Hill, Australia). Frequency and latency of swallow events were calculated. Differences (analysis of variance) are reported for frequency (p < 0.000001) and latency (p < 0.000001). Swallow frequency (mean +/- SD) increased during GC (14.95 +/- 3.02) compared with BL (3.1 +/- 2.85) and PGC (7.0 +/- 2.57). Latency in seconds (mean +/- SD) decreased during GC (24.1 +/- 4.174) and increased with BL (131.8 +/- 59.52) and PGC (mean = 60.74 +/- 25.25). Intertask comparisons (t test) found differences in swallow frequency and latency between tasks: BL vs GC (p < 0.0001, p < 0.0001), BL vs PGC (p < 0.0011, p < 0.0009), and GC vs PGC (p < 0.0001, p < 0.0002), respectively. Post hoc analysis showed carryover to 5.317 minutes. Modifying sensorimotor input by chewing gum alters frequency and latency of swallowing and may be an effective strategy for secretion management in Parkinson disease. This study provides Class III evidence that chewing gum increases swallow frequency and decreases latency of swallowing in an experiment in patients with stage 2 to 4 Parkinson disease who are nonsymptomatic for significant prandial dysphagia.

In situ one-step hydrothermal synthesis of oxygen-containing groups-modified g-C3N4 for the improved photocatalytic H2-evolution performance

NASA Astrophysics Data System (ADS)

Wu, Xinhe; Chen, Fengyun; Wang, Xuefei; Yu, Huogen

2018-01-01

Surface modification of g-C3N4 is one of the most effective strategies to boost its photocatalytic H2-evolution performance via promoting the interfacial catalytic reactions. In this study, an in situ one-step hydrothermal method was developed to prepare the oxygen-containing groups-modified g-C3N4 (OG/g-C3N4) by a facile and green hydrothermal treatment of bulk g-C3N4 in pure water without any additives. It was found that the hydrothermal treatment (180 °C) not only could greatly increase the specific surface area (from 2.3 to 69.8 m2 g-1), but also caused the formation of oxygen-containing groups (sbnd OH and Cdbnd O) on the OG/g-C3N4 surface, via the interlayer delamination and intralayer depolymerization of bulk g-C3N4. Photocatalytic experimental results indicated that after hydrothermal treatment, the resultant OG/g-C3N4 samples showed an obviously improved H2-evolution performance. Especially, when the hydrothermal time was 6 h, the resultant OG/g-C3N4(6 h) exhibited the highest photocatalytic activity, which was clearly higher than that of the bulk g-C3N4 by a factor of ca. 7. In addition to the higher specific surface area, the enhanced H2-evolution rate of OG/g-C3N4 photocatalysts can be mainly attributed to the formation of oxygen-containing groups, which possibly works as the effective H2-evolution active sites. Considering the facie and green synthesis method, the present work may provide a new insight for the development of highly efficient photocatalytic materials.

Multiresidue determination of pesticides in tea by gas chromatography-tandem mass spectrometry.

PubMed

Saito-Shida, Shizuka; Nemoto, Satoru; Teshima, Reiko

2015-01-01

An efficient and reliable GC-MS/MS method for the multiresidue determination of pesticides in tea was developed by modifying the Japanese official multiresidue method. Sample preparation was carefully optimized for the efficient removal of coextracted matrix components. The optimal sample preparation procedure involved swelling of the sample in water; extraction with acetonitrile; removal of water by salting-out; and sequential cleanup by ODS, graphitized carbon black/primary secondary amine (GCB/PSA) and silica gel cartridges prior to GC-MS/MS analysis. The recoveries of 162 pesticides from fortified (at 0.01 mg kg(-1)) green tea, oolong tea, black tea and matcha (powdered green tea) were mostly (95-98% of the tested pesticides) within the range of 70-120%, with relative standard deviations of <20%. Poor recovery of triazole pesticides was considered to be due to low recovery from the silica gel cartridges. The test solutions obtained by the modified method contained relatively small amounts of pigments, caffeine and other matrix components and were cleaner than those obtained by the original Japanese official multiresidue method. No interfering peaks were observed in the blank chromatograms, indicating the high selectivity of the modified method. The overall results suggest that the developed method is suitable for the quantitative analysis of GC-amenable pesticide residues in tea.

Reduction-oxidation Enabled Glass-ceramics to Stainless Steel Bonding Part I: screening of doping oxidants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Steve Xunhu

Lithium silicate-based glass-ceramics with high coefficients of thermal expansion, designed to form matched hermetic seals in 304L stainless steel housing, show little evidence of interfacial chemical bonding, despite extensive inter-diffusion at the glass-ceramic-stainless steel (GC-SS) interface. A series of glass-ceramic compositions modified with a variety of oxidants, AgO, FeO, NiO, PbO, SnO, CuO, CoO, MoO 3 and WO 3, are examined for the feasibility of forming bonding oxides through reduction-oxidation (redox) at the GC-SS interface. The oxidants were selected according to their Gibbs free energy to allow for oxidation of Cr/Mn/Si from stainless steel, and yet to prevent a reductionmore » of P2O5 in the glass-ceramic where the P 2O 5 is to form Li 3PO 4 nuclei for growth of high expansion crystalline SiO 2 phases. Other than the CuO and CoO modified glass-ceramics, bonding from interfacial redox reactions were not achieved in the modified glass-ceramics, either because of poor wetting on the stainless steel or a reduction of the oxidants at the surface of glass-ceramic specimens rather than the GC-SS interface.« less

An Application of Passive Samplers to Understand Atmospheric Mercury Concentration and Dry Deposition Spatial Distributions

EPA Science Inventory

Two modified passive samplers were evaluated at multiple field locations. The sampling rate (SR) of the modified polyurethane foam (PUF)-disk passive sampler for total gaseous mercury (TGM) using gold-coated quartz fiber filters (GcQFF) and gaseous oxidized mercury (GOM) using io...

Highly sensitive and simultaneous electrochemical determination of 2-aminophenol and 4-aminophenol based on poly(l-arginine)-β-cyclodextrin/carbon nanotubes@graphene nanoribbons modified electrode.

PubMed

Yi, Yinhui; Zhu, Gangbing; Wu, Xiangyang; Wang, Kun

2016-03-15

Owing to the similar characteristics and physiochemical property of 2-aminophenol (2-AP) and 4-aminophenol (4-AP), the highly sensitive simultaneous electrochemical determination of 2- and 4-AP is a great challenge. In this paper, by electropolymerizing β-cyclodextrin (β-CD) and l-arginine (l-Arg) on the surface of carbon nanotubes@graphene nanoribbons (CNTs@GNRs) core-shell heterostructure, a P-β-CD-l-Arg/CNTs@GNRs nanohybrid modified electrode was prepared successfully, and it could exhibit the synergetic effects of β-CD (high host-guest recognition and enrichment ability), l-Arg (excellent electrocatalytic activity) and CNTs@GNRs (prominent electrochemical properties and large surface area), the P-β-CD-l-Arg/CNTs@GNRs modified electrode was used in the electrochemical determination of 2- and 4-AP, the results demonstrated that the highly sensitive and simultaneous determination of 2- and 4-AP is successfully achieved and the modified electrode has a linear response range of 25.0-1300.0 nM for both 2- and 4-AP, and the detection limits of 2- and 4-AP obtained in this work are 6.2 and 3.5 nM, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Determination of functionalized gold nanoparticles incorporated in hydrophilic and hydrophobic microenvironments by surface modification of quartz crystal microbalance

NASA Astrophysics Data System (ADS)

Wu, Tsui-Hsun; Liao, Shu-Chuan; Chen, Ying-Fang; Huang, Yi-You; Wei, Yi-Syuan; Tu, Shu-Ju; Chen, Ko-Shao

2013-06-01

In this study, plasma deposition methods were used to immobilize Au electrode of a quartz crystal microbalance (QCM) to create different microenvironments for mass measurement of various modified Au nanoparticles (AuNPs). AuNPs were modified by 11-mercaptoundecanoic acid (MUA) and 1-decanethiol (DCT) for potential applications to drug release, protective coatings, and immunosensors. We aimed to develop a highly sensitive and reliable method to quantify the mass of various modified AuNPs. The surface of AuNPs and Au electrode was coated with polymer films, as determined by Fourier transform infrared spectroscopy and atomic force microscopy. Measurements obtained for various AuNPs and the plasma-treated surface of the Au electrode were compared with those obtained for an untreated Au electrode. According to the resonant frequency shift of QCM, a linear relationship was observed that significantly differed for AuNPs, MUA-AuNPs, and DCT-AuNPs (R2 range, 0.94-0.965, 0.934-0.972, and 0.874-0.9514, respectively). Compared to inductively coupled plasma and micro-computerized tomography, the QCM method with plasma treatment has advantages of real-time monitoring, greater sensitivity, and lower cost. Our results demonstrate that surface modifications measured by a QCM system for various modified AuNPs were reliable.

Modified coaxial wire method for measurement of transfer impedance of beam position monitors

NASA Astrophysics Data System (ADS)

Kumar, Mukesh; Babbar, L. K.; Deo, R. K.; Puntambekar, T. A.; Senecha, V. K.

2018-05-01

The transfer impedance is a very important parameter of a beam position monitor (BPM) which relates its output signal with the beam current. The coaxial wire method is a standard technique to measure transfer impedance of the BPM. The conventional coaxial wire method requires impedance matching between coaxial wire and external circuits (vector network analyzer and associated cables). This paper presents a modified coaxial wire method for bench measurement of the transfer impedance of capacitive pickups like button electrodes and shoe box BPMs. Unlike the conventional coaxial wire method, in the modified coaxial wire method no impedance matching elements have been used between the device under test and the external circuit. The effect of impedance mismatch has been solved mathematically and a new expression of transfer impedance has been derived. The proposed method is verified through simulation of a button electrode BPM using cst studio suite. The new method is also applied to measure transfer impedance of a button electrode BPM developed for insertion devices of Indus-2 and the results are also compared with its simulations. Close agreement between measured and simulation results suggests that the modified coaxial wire setup can be exploited for the measurement of transfer impedance of capacitive BPMs like button electrodes and shoe box BPM.

Sensitive, selective, disposable electrochemical dopamine sensor based on PEDOT-modified laser scribed graphene.

PubMed

Xu, Guangyuan; Jarjes, Zahraa A; Desprez, Valentin; Kilmartin, Paul A; Travas-Sejdic, Jadranka

2018-06-01

The fabrication of a novel, and highly selective electrochemical sensor based on a poly(3,4-ethylenedioxythiophene) (PEDOT) modified laser scribed graphene (LSG), and detection of dopamine (DA) in the presence of ascorbic acid (AA) and uric acid (UA) is described. LSG electrodes were produced with a 3-dimensional macro-porous network and large electrochemically-active surface area via direct laser writing on polyimide sheets. PEDOT was electrodeposited on the LSG electrode, and the physical properties of the obtained films were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray diffraction microanalysis (EDAX). The modified electrodes were applied for the determination of DA in the presence of AA and UA using cyclic voltammetry (CV), and differential pulse voltammetry (DPV) techniques. The linear range for dopamine detection was found to be 1-150 µM with a sensitivity of 0.220 ± 0.011 µA μM -1 and a detection limit of 0.33 µM; superior values to those obtained without PEDOT. For the first time, PEDOT-modified LSG have been fabricated and assessed for high-performance dopamine sensing using cost-effective, disposable electrodes, with potential for development in further sensing applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Immobilization of ruthenium phthalocyanine on silica-coated multi-wall partially oriented carbon nanotubes: Electrochemical detection of fenitrothion pesticide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Canevari, Thiago C., E-mail: tccanevari@gmail.com; Prado, Thiago M.; Cincotto, Fernando H.

Highlights: • Hybrid material, SiO{sub 2}/MWCNTs containing ruthenium phthalocyanine (RuPc) synthesized in situ. • Silica containing multi-walled carbon nanotube partially oriented. • Determination of pesticide fenitrothion in orange juice. - Abstract: This paper reports on the determination of the pesticide fenitrothion using a glassy carbon electrode modified with silica-coated, multi-walled, partially oriented carbon nanotubes, SiO{sub 2}/MWCNTs, containing ruthenium phthalocyanine (RuPc) synthesized in situ. The hybrid SiO{sub 2}/MWCNTs/RuPc material was characterized by UV–vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and differential pulse voltammetry. The modified electrode showed well-defined peaks in the presencemore » of fenitrothion in acetate buffer, pH 4.5, with a sensitivity of 0.0822 μA μM{sup −1} mm{sup −2} and a detection limit of 0.45 ppm. Notably, the modified SiO{sub 2}/MWCNTs/RuPc electrodes with did not suffer from significant influences in the presence of other organophosphorus pesticides during the determination of the fenitrothion pesticide. Moreover, this modified electrode showed excellent performance in the determination of fenitrothion in orange juice.« less

Amplified electrochemiluminescence of quantum dots by electrochemically reduced graphene oxide for nanobiosensing of acetylcholine.

PubMed

Deng, Shengyuan; Lei, Jianping; Cheng, Lingxiao; Zhang, Yangyang; Ju, Huangxian

2011-07-15

A signal amplification system for electrochemiluminescence (ECL) of quantum dots (QDs) was developed by using electrochemically reduced graphene oxide (ERGO) to construct a nanobiosensing platform. Due to the structural defects of GO, the ECL emission of QDs coated on GO modified electrode was significantly quenched. After the electrochemical reduction of GO, the restoration of structural conjugation was observed with spectroscopic, morphologic and impedance techniques. Thus in the presence of dissolved O₂ as coreactant, the QDs/ERGO modified electrode showed ECL intensity increase by 4.2 and 178.9 times as compared with intrinsic QDs and QDs/GO modified electrodes due to the adsorption of dissolved O₂ on ERGO and the facilitated electron transfer. After choline oxidase (ChO) or ChO-acetylcholinesterase was further covalently cross-linked on the QDs/ERGO modified electrode, two ECL biosensors for choline and acetylcholine were fabricated, which showed the linear response ranges and detection limits of 10-210 μM and 8.8 μM for choline, and 10-250 μM and 4.7 μM for acetylcholine, respectively. This green and facile approach to prepare graphene-QDs system could be of potential applications in electronic device and bioanalysis. Copyright © 2011 Elsevier B.V. All rights reserved.

Synthesis of water soluble chitosan stabilized gold nanoparticles and determination of uric acid

NASA Astrophysics Data System (ADS)

Lanh Le, Thi; Khieu Dinh, Quang; Hoa Tran, Thai; Nguyen, Hai Phong; Le Hien Hoang, Thi; Hien Nguyen, Quoc

2014-06-01

Gold nanoparticles (Au-NPs) have been successfully synthesized by utilizing water soluble chitosan as reducing and stabilizing agent. The colloidal Au-NPs were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). The results showed that the colloidal Au-NPs had a plasmon absorption band with maximum wavelength in the range of 520-526 nm and the diameters were about 8-15 nm. In addition, a new Au-NPs-modified electrode was fabricated by self-assembling Au-NPs to the surface of the L-cysteine-modified glassy carbon electrode (Au-NPs/L-Cys/GCE). The Au-NPs-modified electrode showed an excellent character for electro-catalytic oxidization of uric acid (UA) in 0.1 mol L-1 phosphate buffer solution (pH 3.2). Using differential pulse anodic stripping voltammetry (DP-ASV), a high selectivity for determination of UA has been explored for the Au-NPs-modified electrode. DP-ASV peak currents of UA increased linearly with their concentration at the range of 2.0 × 10-6 to 4.0 × 10-5 mol L-1 with the detection limit of 2.7 × 10-6 mol L-1 for UA. The proposed method was applied for the detection of UA in human urine and serum samples with satisfactory results.

Fabrication and characterization of PbO2 electrode modified with [Fe(CN)6](3-) and its application on electrochemical degradation of alkali lignin.

PubMed

Hao, Xu; Quansheng, Yuan; Dan, Shao; Honghui, Yang; Jidong, Liang; Jiangtao, Feng; Wei, Yan

2015-04-09

PbO2 electrode modified by [Fe(CN)6](3-) (marked as FeCN-PbO2) was prepared by electro-deposition method and used for the electrochemical degradation of alkali lignin (AL). The surface morphology and the structure of the electrodes were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD), respectively. The stability and electrochemical activity of FeCN-PbO2 electrode were characterized by accelerated life test, linear sweep voltammetry, electrochemical impedance spectrum (EIS) and AL degradation. The results showed that [Fe(CN)6](3-) increased the average grain size of PbO2 and formed a compact surface coating. The service lifetime of FeCN-PbO2 electrode was 287.25 h, which was longer than that of the unmodified PbO2 electrode (100.5h). The FeCN-PbO2 electrode showed higher active surface area and higher oxygen evolution potential than that of the unmodified PbO2 electrode. In electrochemical degradation tests, the apparent kinetics coefficient of FeCN-PbO2 electrode was 0.00609 min(-1), which was higher than that of unmodified PbO2 electrode (0.00419 min(-1)). The effects of experimental parameters, such as applied current density, initial AL concentration, initial pH value and solution temperature, on electrochemical degradation of AL by FeCN-PbO2 electrode were evaluated. Copyright © 2015 Elsevier B.V. All rights reserved.

A ω-mercaptoundecylphosphonic acid chemically modified gold electrode for uranium determination in waters in presence of organic matter.

PubMed

Merli, Daniele; Protti, Stefano; Labò, Matteo; Pesavento, Maria; Profumo, Antonella

2016-05-01

A chemically modified electrode (CME) on a gold surface assembled with a ω-phosphonic acid terminated thiol was investigated for its capability to complex uranyl ions. The electrode, characterized by electrochemical techniques, demonstrated to be effective for the determination of uranyl at sub-μgL(-1) level by differential pulse adsorptive stripping voltammetry (DPAdSV) in environmental waters, also in presence of humic matter and other potential chelating agents. The accuracy of the measurements was investigated employing as model probes ligands of different complexing capability (humic acids and EDTA). Copyright © 2016 Elsevier B.V. All rights reserved.

Novel ferrocene-anchored ZnO nanoparticle/carbon nanotube assembly for glucose oxidase wiring: application to a glucose/air fuel cell.

PubMed

Haddad, Raoudha; Mattei, Jean-Gabriel; Thery, Jessica; Auger, Aurélien

2015-06-28

Glucose oxidase (GOx) is immobilized on ZnO nanoparticle-modified electrodes. The immobilized glucose oxidase shows efficient mediated electron transfer with ZnO nanoparticles to which the ferrocenyl moiety is π-stacked into a supramolecular architecture. The constructed ZnO-Fc/CNT modified electrode exhibits high ferrocene surface coverage, preventing any leakage of the π-stacked ferrocene from the newly described ZnO hybrid nanoparticles. The use of the new architecture of ZnO supported electron mediators to shuttle electrons from the redox centre of the enzyme to the surface of the working electrode can effectively bring about successful glucose oxidation. These modified electrodes evaluated as a highly efficient architecture provide a catalytic current for glucose oxidation and are integrated in a specially designed glucose/air fuel cell prototype using a conventional platinum-carbon (Pt/C) cathode at physiological pH (7.0). The obtained architecture leads to a peak power density of 53 μW cm(-2) at 300 mV for the Nafion® based biofuel cell under "air breathing" conditions at room temperature.

Immobilization of nanobeads on a surface to control the size, shape and distribution of pores in electrochemically generated sol-gel films.

PubMed

Ciabocco, Michela; Berrettoni, Mario; Zamponi, Silvia; Cox, James A

2015-07-01

Electrochemically assisted deposition of an ormosil film at a potential where hydrogen ion is generated as the catalyst yields insulating films on electrodes. When the base electrode is modified with 20-nm poly(styrene sulfonate), PSS, beads bound to the surface with 3-aminopropyltriethoxysilane (APTES) and using (CH 3 ) 3 SiOCH 3 as the precursor, the resulting film of organically modified silica (ormosil) has cylindrical channels that reflect both the diameter of the PSS and the distribution of the APTES-PSS on the electrode. At an electrode modified by a 20-min immersion in 0.5 mmol dm -3 APTES followed by a 30-s immersion in PSS, a 20-min electrolysis at 1.5 V in acidified (CH 3 ) 3 SiOCH 3 resulted in an ormosil film with 20-nm pores separated by 100 nm. Cyclic voltammetry of Ru(CN) 6 4- at scan rates above 5 mVs -1 yielded currents controlled primarily by linear diffusion. Below 5 mVs -1 , convection rather than the expected factor, radial diffusion, apparently limited the current.

Determination of bisphenol A in food-simulating liquids using LCED with a chemically modified electrode.

PubMed

D'Antuono, A; Dall'Orto, V C; Lo Balbo, A; Sobral, S; Rezzano, I

2001-03-01

Liquid chromatography with electrochemical detector (LC-ED), using a chemically modified electrode coated with a metalloporphyrin film, is reported for determination of bisphenol A (BPA) migration from polycarbonate baby bottles. The extraction process of the samples was performed according to regulations of the Southern Common Market (MERCOSUR), where certain food-simulating liquids [(A) distilled water, (B) acetic acid 3% V/V in distilled water, and (C) ethanol 15% V/V in distilled water] are defined along with controlled time and temperature conditions. The baseline obtained using the naked electrode showed a considerable drift which increased the detection limit. This effect was suppressed with the chemically modified electrode. A linear range up to 450 ppb along with a detection limit of 20 ppb for the amperometric detection technique was observed. The procedure described herein allowed lowering the detection limit of the method to 0.2 ppb. The value found for BPA in the food-simulating liquid is 1.2 ppb, which is below the tolerance limit for specific migration (4.8 ppm).

Effect of NaX zeolite-modified graphite felts on hexavalent chromium removal in biocathode microbial fuel cells.

PubMed

Wu, Xiayuan; Tong, Fei; Yong, Xiaoyu; Zhou, Jun; Zhang, Lixiong; Jia, Honghua; Wei, Ping

2016-05-05

Two kinds of NaX zeolite-modified graphite felts were used as biocathode electrodes in hexavalent chromium (Cr(VI))-reducing microbial fuel cells (MFCs). The one was fabricated through direct modification, and the other one processed by HNO3 pretreatment of graphite felt before modification. The results showed that two NaX zeolite-modified graphite felts are excellent bio-electrode materials for MFCs, and that a large NaX loading mass, obtained by HNO3 pretreatment (the HNO3-NaX electrode), leads to a superior performance. The HNO3-NaX electrode significantly improved the electricity generation and Cr(VI) removal of the MFC. The maximum Cr(VI) removal rate increased to 10.39±0.28 mg/L h, which was 8.2 times higher than that of the unmodified control. The improvement was ascribed to the strong affinity that NaX zeolite particles, present in large number on the graphite felt, have for microorganisms and Cr(VI) ions. Copyright © 2016 Elsevier B.V. All rights reserved.

A voltammetric method for Fe(iii) in blood serum using a screen-printed electrode modified with a Schiff base ionophore.

PubMed

Mittal, Susheel K; Rana, Sonia; Kaur, Navneet; Banks, Craig E

2018-05-23

Herein, a potent electrochemical ionophore (SMS-2) based on a Schiff base has been used for the modification of a screen-printed electrode (SPE). The modified disposable electrode can selectively detect ferric ions in an aqueous medium. Redox behavior of the proposed strip was characterized using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Incorporation of the ligand in the ink of the SPE enhanced the analytical performance of the electrode, and its surface modification was confirmed by SEM and EDX analysis. Shifting/quenching of the cathodic peak potential of the ionophore after binding with Fe(iii) ions was used to detect and measure the ferric ion concentration. This sensor can identify Fe(iii) in the detection range from 0.625 μM to 7.5 μM. The modified SPE can selectively detect ferric ions in the presence of many other interfering ions and has been successfully used to determine the Fe(iii) content in blood serum samples. The metal-ionophore complex structure was optimized using DFT calculations to study the energetics of the metal-ionophore interactions.

Electrochemical response of carbon paste electrode modified with mixture of titanium dioxide/zirconium dioxide in the detection of heavy metals: lead and cadmium.

PubMed

Nguyen, Phuong Khanh Quoc; Lunsford, Suzanne K

2012-11-15

A novel carbon modified electrode was developed by incorporating titanium dioxide/zirconium dioxide into the graphite carbon paste electrode to detect heavy metals-cadmium and lead. In this work, the development of the novel titanium dioxide/zirconium dioxide modified carbon paste electrode was studied to determine the optimum synthesis conditions related to the temperature, heating duration, amount and ratio of titanium dioxide/zirconium dioxide, and amount of surfactant, to create the most reproducible results. Using cyclic voltammetric (CV) analysis, this study has proven that the novel titanium dioxide/zirconium dioxide can be utilized to detect heavy metals-lead and cadmium, at relatively low concentrations (7.6×10(-6) M and 1.1×10(-5) M for Pb and Cd, respectively) at optimum pH value (pH=3). From analyzing CV data the optimal electrodes surface area was estimated to be 0.028 (±0.003) cm(2). Also, under the specific experimental conditions, electron transfer coefficients were estimated to be 0.44 and 0.33 along with the heterogeneous electron transfer rate constants of 5.64×10(-3) and 2.42×10(-3) (cm/s) for Pb and Cd, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrochemistry of hemoglobin entrapped in a Nafion/nano-ZnO film on carbon ionic liquid electrode.

PubMed

Sun, Wei; Zhai, ZiQin; Wang, DanDan; Liu, ShuFeng; Jiao, Kui

2009-02-01

A stable composite film composed of the ionomer Nafion, the ZnO nanoparticle and the protein hemoglobin was cast on the surface of an ionic liquid modified carbon paste electrode (CILE) to establish a modified electrode denoted as Nafion/nano-ZnO/Hb/CILE. UV-vis and FT-IR spectrum showed that hemoglobin in the film retained its native conformation. The electrochemical behaviors of hemoglobin entrapped in the film were carefully investigated with cyclic voltammetry. A pair of well-defined and quasi-reversible redox voltammetric peaks for Hb Fe(III)/Fe(II) was obtained with the standard potential (E(0)') located at -0.344 V (vs. SCE) in phosphate buffer solution (PBS, pH 7.0), which was attributed to the direct electron transfer of Hb with electrode in the microenvironments of ZnO nanoparticle and ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF(6)). The electrochemical parameters of Hb in the composite film were further carefully calculated with the results of the electron-transfer rate constant (k(s)) as 0.139 s(-1), the charge transfer coefficient (alpha) as 0.413 and the number of electron transferred (n) as 0.95. The Hb modified electrode showed good electrocatalytic ability toward the reduction of trichloroacetic acid (TCA).

Modified Au nanoparticles-imprinted sol-gel, multiwall carbon nanotubes pencil graphite electrode used as a sensor for ranitidine determination.

PubMed

Rezaei, B; Lotfi-Forushani, H; Ensafi, A A

2014-04-01

A new, simple, and disposable molecularly imprinted electrochemical sensor for the determination of ranitidine was developed on pencil graphite electrode (PGE) via cyclic voltammetry (CV). The PGEs were coated with MWCNTs containing the carboxylic functional group (f-MWCNTs), imprinted with sol-gel and Au nanoparticle (AuNPs) layers (AuNP/MIP-sol-gel/f-MWCNT/PGE), respectively, to enhance the electrode's electrical transmission and sensitivity. The thin film of molecularly imprinted sol-gel polymers with specific binding sites for ranitidine was cast on modified PGE by electrochemical deposition. The AuNP/MIP-sol-gel/f-MWCNT/PGE thus developed was characterized by electrochemical impedance spectroscopy (EIS) and CV. The interaction between the imprinted sensor and the target molecule was also observed on the electrode by measuring the current response of 5.0mMK3[Fe(CN)6] solution as an electrochemical probe. The pick currents of ranitidine increased linearly with concentration in the ranges of 0.05 to 2.0μM, with a detection limit of (S/N=3) 0.02μM. Finally, the modified electrode was successfully employed to determine ranitidine in human urine samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Enhanced electrocatalytic oxidation of isoniazid at electrochemically modified rhodium electrode for biological and pharmaceutical analysis.

PubMed

Cheemalapati, Srikanth; Chen, Shen-Ming; Ali, M Ajmal; Al-Hemaid, Fahad M A

2014-09-01

A simple and sensitive electrochemical method has been proposed for the determination of isoniazid (INZ). For the first time, rhodium (Rh) modified glassy carbon electrode (GCE) has been employed for the determination of INZ by linear sweep voltammetry technique (LSV). Compared with the unmodified electrode, the proposed Rh modified electrode provides strong electrocatalytic activity toward INZ with significant enhancement in the anodic peak current. Scanning electron microscopy (SEM) and field emission scanning electron microscopy (FESEM) results reveal the morphology of Rh particles. With the advantages of wide linearity (70-1300μM), good sensitivity (0.139μAμM(-1)cm(-2)) and low detection limit (13μM), this proposed sensor holds great potential for the determination of INZ in real samples. The practicality of the proposed electrode for the detection of INZ in human urine and blood plasma samples has been successfully demonstrated using LSV technique. Through the determination of INZ in commercially available pharmaceutical tablets, the practical applicability of the proposed method has been validated. The recovery results are found to be in good agreement with the labeled amounts of INZ in tablets, thus showing its great potential for use in clinical and pharmaceutical analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

Modification of Glucose Oxidase biofuel cell by multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Lotfi, Ladan; Farahbakhsh, Afshin; Aghili, Sina

2018-01-01

Biofuel cells are a subset of fuel cells that employ biocatalysts. Enzyme-based biofuel cells (EBFCs) generate electrical energy from biofuels such as glucose and ethanol, which are renewable and sustainable energy sources. Glucose biofuel cells (GBFCs) are particularly interesting nowadays due to continuous harvesting of oxygen and glucose from bioavailable substrates, activity inside the human body, and environmental benign, which generate electricity through oxidation of glucose on the anode and reduction of oxygen on the cathode. Promoting the electron transfer of redox enzymes at modified electrode utilizing Nano size materials, such as carbon nanotubes (CNT), to achieve the direct electrochemistry of enzymes has been reported. The polypyrrole-MWCNTs-glucose oxidase (PY-CNT-GOx) electrode has been investigated in the present work. Cyclic voltammetry tests were performed in a three-electrode electrochemical set-up with modified electrode (Pt/PPy/MWCNTs/GOx) was used as working electrode. Platinum flat and Ag/AgCl (saturated KCl) were used as counter electrode and the reference electrode, respectively. The biofuel cells probe was prepared by immobilizing MWCNTs at the tip of a platinum (Pt) electrode (0.5 cm2) with PPy as the support matrix We have demonstrated a well-dispersed nanomaterial PPy/MWNT, which is able to immobilize GOx firmly under the condition of the absence of any other cross-linking agent.

An improved amperometric creatinine biosensor based on nanoparticles of creatininase, creatinase and sarcosine oxidase.

PubMed

Kumar, Parveen; Jaiwal, Ranjana; Pundir, C S

2017-11-15

An improved amperometric biosensor for detection of creatinine was developed based on immobilization of nanoparticles (NPs) of creatininase (CA), creatinase (CI), and sarcosine oxidase (SOx) onto glassy carbon (GC) electrode. Transmission electron microscopy (TEM) and fourier transform infrared spectroscopy (FTIR) were employed for characterization of enzyme nanoparticles (ENPs). The GC electrode was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) at different stages of its amendment. The biosensor showed optimum response within 2s at pH 6.0 in 0.1 M sodium phosphate buffer and 25 °C, when operated at 1.0 V against Ag/AgCl. Biosensor exhibited wider linear range from 0.01 μM to 12 μM with a limit of detection (LOD) of 0.01 μM. The analytical recoveries of added creatinine in sera were 97.97 ± 0.1% for 0.1 mM and 98.76 ± 0.2% for 0.15 mM, within and between batch coefficients of variation (CV) were 2.06% and 3.09% respectively. A good correlation (R 2  = 0.99) was observed between sera creatinine values obtained by standard enzymic colorimetric method and the present biosensor. This biosensor measured creatinine level in sera of apparently healthy subjects and persons suffering from renal and muscular dysfunction. The ENPs electrode lost 10% of its initial activity within 240 days of its regular uses, when stored at 4 °C. Copyright © 2017 Elsevier Inc. All rights reserved.

Electrochemical study of ricin at glassy carbon electrode.

PubMed

Ribeiro, Williame F; da Costa, Daniel J E; Lourenço, Anabel S; Lopes, Ilanna C; de Medeiros, Everaldo P; Salazar-Banda, Giancarlo R; do Nascimento, Valberes B; de Araújo, Mário C U

2013-08-21

Ricin, Ricinus communis agglutinin 60 - RCA 60, is a deadly phytotoxic protein which inhibits ribosomes (class II), and there is no known effective antidote in living organisms. Ricin is composed of two polypeptide chains, A and B, linked covalently by a single disulfide bond. The analytical methods for the detection of RCA 60 are commonly laborious, expensive, require skilled labor, and involve sophisticated equipment. Aimed at the development of electroanalytical methods for RCA 60 detection, here we studied the electrochemical oxidation of RCA 60 on a glassy carbon (GC) electrode over a wide pH range, using cyclic voltammetry, differential pulse voltammetry (DPV) and square wave voltammetry (SWV). Two quasi-reversible electrochemical RCA 60 oxidation peaks were identified on the GC electrode by SWV. For values of 2.2 ≤ pH ≤ 10.2, DPV studies revealed that the peak potentials, EP1 and EP2, display a linear dependence with pH and the reaction mechanism involves the transfer of 2H⁺/2e⁻ (peak 1) and 1H⁺/1e⁻ (peak 2). The first and second RCA 60 oxidation steps may correspond to the oxidation of cysteine and tyrosine-tryptophan residues, respectively. The oxidation product of the second RCA 60 oxidation step appears at 7.0 ≤ pH ≤ 11.8. For pH ≥ 10.2, both processes are pH independent, resulting in a pKa of ca. 10.2. A third RCA 60 oxidation peak only appears at acidic pH. RCA 60 samples extracted from different castor seed cultivars showed similar electrochemical behavior, enabling the implementation of an analytical voltammetric method.

Biosensors Based on Urease Adsorbed on Nickel, Platinum, and Gold Conductometric Transducers Modified with Silicalite and Nanozeolites

NASA Astrophysics Data System (ADS)

Kucherenko, Ivan S.; Soldatkin, Oleksandr O.; Kasap, Berna Ozansoy; Kurç, Burcu Akata; Melnyk, Volodymir G.; Semenycheva, Lyudmila M.; Dzyadevych, Sergei V.; Soldatkin, Alexei P.

This work describes urease-based conductometric biosensors that were created using nontypical method of urease immobilization via adsorption on micro- and nanoporous particles: silicalite and nanocrystalline zeolites Beta (BEA) and L. Conductometric transducers with nickel, gold, and platinum interdigitated electrodes were used. Active regions of the nickel transducers were modified with microparticles using two procedures—spin coating and drop coating. Gold and platinum transducers were modified with silicalite using drop coating since it was more effective. Scanning electron microscopy was used to evaluate effectiveness of these procedures. The procedure of spin coating produced more uniform layers of particles (and biosensors had good reproducibility of preparation), but it was more complicated, drop coating was easier and led to formation of a bulk of particles; thus, biosensors had bigger sensitivity but worse reproducibility of preparation. Urease was immobilized onto transducers modified with particles by physical adsorption. Analytical characteristics of the obtained biosensors for determination of urea (calibration curves, sensitivity, limit of detection, linear concentration range, noise of responses, reproducibility of signal during a day, and operational stability during 3 days) were compared. Biosensors with all three particles deposited by spin coating showed similar characteristics; however, silicalite was a bit more effective. Biosensors based on nickel transducers modified by drop coating had better characteristics in comparison with modification by spin coating (except reproducibility of preparation). Transducers with gold electrodes showed best characteristics while creating biosensors, platinum electrodes were slightly inferior to them, and nickel electrodes were the worst.

Graphitic carbon nitride (g-C3N4) coated titanium oxide nanotube arrays with enhanced photo-electrochemical performance.

PubMed

Sun, Mingxuan; Fang, Yalin; Kong, Yuanyuan; Sun, Shanfu; Yu, Zhishui; Umar, Ahmad

2016-08-09

Herein, we report the successful formation of graphitic carbon nitride coated titanium oxide nanotube array thin films (g-C3N4/TiO2) via the facile thermal treatment of anodized Ti sheets over melamine. The proportion of C3N4 and TiO2 in the composite can be adjusted by changing the initial addition mass of melamine. The as-prepared samples are characterized by several techniques in order to understand the morphological, structural, compositional and optical properties. UV-vis absorption studies exhibit a remarkable red shift for the g-C3N4/TiO2 thin films as compared to the pristine TiO2 nanotubes. Importantly, the prepared composites exhibit an enhanced photocurrent and photo-potential under both UV-vis and visible light irradiation. Moreover, the observed maximum photo-conversion efficiency of the prepared composites is 1.59 times higher than that of the pristine TiO2 nanotubes. The optical and electrochemical impedance spectra analysis reveals that the better photo-electrochemical performance of the g-C3N4/TiO2 nanotubes is mainly due to the wider light absorption and reduced impedance compared to the bare TiO2 nanotube electrode. The presented work demonstrates a facile and simple method to fabricate g-C3N4/TiO2 nanotubes and clearly revealed that the introduction of g-C3N4 is a new and innovative approach to improve the photocurrent and photo-potential efficiencies of TiO2.

A nitric oxide/cysteine interaction mediates the activation of soluble guanylate cyclase

PubMed Central

Fernhoff, Nathaniel B.; Derbyshire, Emily R.; Marletta, Michael A.

2009-01-01

Nitric oxide (NO) regulates a number of essential physiological processes by activating soluble guanylate cyclase (sGC) to produce the second messenger cGMP. The mechanism of NO sensing was previously thought to result exclusively from NO binding to the sGC heme; however, recent studies indicate that heme-bound NO only partially activates sGC and additional NO is involved in the mechanism of maximal NO activation. Furthermore, thiol oxidation of sGC cysteines results in the loss of enzyme activity. Herein the role of cysteines in NO-stimulated sGC activity investigated. We find that the thiol modifying reagent methyl methanethiosulfonate specifically inhibits NO activation of sGC by blocking a non-heme site, which defines a role for sGC cysteine(s) in mediating NO binding. The nature of the NO/cysteine interaction was probed by examining the effects of redox active reagents on NO-stimulated activity. These results show that NO binding to, and dissociation from, the critical cysteine(s) does not involve a change in the thiol redox state. Evidence is provided for non-heme NO in the physiological activation of sGC in context of a primary cell culture of human umbilical vein endothelial cells. These findings have relevance to diseases involving the NO/cGMP signaling pathway. PMID:20007374

Remarkable sensitivity for detection of bisphenol A on a gold electrode modified with nickel tetraamino phthalocyanine containing Ni-O-Ni bridges.

PubMed

Chauke, Vongani; Matemadombo, Fungisai; Nyokong, Tebello

2010-06-15

This work reports the electrocatalysis of bisphenol A on Ni(II) tetraamino metallophthalocyanine (NiTAPc) polymer modified gold electrode containing Ni-O-Ni bridges (represented as Ni(OH)TAPc). The Ni(II)TAPc films were electro-transformed in 0.1 mol L(-1) NaOH aqueous solution to form 'O-Ni-O oxo bridges', forming poly-n-Ni(OH)TAPc (where n is the number of polymerising scans). poly-30-Ni(OH)TAPc, poly-50-Ni(OH)TAPc, poly-70-Ni(OH)TAPc and poly-90-Ni(OH)TAPc films were investigated. The polymeric films were characterised by electrochemical impedance spectroscopy and the charge transfer resistance (R(CT)) values increased with film thickness. The best catalytic activity for the detection of bisphenol A was on poly-70-Ni(OH)TAPc. Electrode resistance to passivation improved with polymer thickness. The electrocatalytic behaviour of bisphenol A was compared to that of p-nitrophenol in terms of electrode passivation and regeneration. The latter was found to passivate the electrode less than the former. The poly-70-Ni(OH)TAPc modified electrode could reliably detect bisphenol A in a concentration range of 7x10(-4) to 3x10(-2)mol L(-1) with a limit of detection of 3.68x10(-9)mol L(-1). The sensitivity was 3.26x10(-4)A mol(-1) L cm(-2). Copyright 2010 Elsevier B.V. All rights reserved.

A novel rapid synthesis of Fe{sub 2}O{sub 3}/graphene nanocomposite using ferrate(VI) and its application as a new kind of nanocomposite modified electrode as electrochemical sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karimi, Mohammad Ali, E-mail: ma_karimi43@yahoo.com; Department of Chemistry & Nanoscience and Nanotechnology Research Laboratory; Banifatemeh, Fatemeh

2015-10-15

Highlights: • A novel rapid synthesis of rGO–Fe{sub 2}O{sub 3} nanocomposite was developed using Fe(VI). • Fe(VI) as an environmentally friendly oxidant was introduced for GO synthesis. • Synthesized rGO–Fe{sub 2}O{sub 3} nanocomposite was applied as electrochemical sensor. • A non-enzymatic sensor was developed for H{sub 2}O{sub 2}. - Abstract: In this study, a novel, simple and sensitive non-enzymatic hydrogen peroxide electrochemical sensor was developed using reduced graphene oxide/Fe{sub 2}O{sub 3} nanocomposite modified glassy carbon electrode. This nanocomposite was synthesized by reaction of sodium ferrate with graphene in alkaline media. This reaction completed in 5 min and the products weremore » stable and its deposition on the surface of electrode is investigated. It has been found the apparent charge transfer rate constant (ks) is 0.52 and transfer coefficient (α) is 0.61 for electron transfer between the modifier and glassy carbon electrode. Electrochemical behavior of this electrode and its ability to catalyze the electro-reduction of H{sub 2}O{sub 2} has been studied by cyclic voltammetry and chronoamperometry at different experimental conditions. The analytical parameters showed the good ability of electrode as a sensor for H{sub 2}O{sub 2} amperometric reduction.« less

Switchable silver mirrors with long memory effects.

PubMed

Park, Chihyun; Seo, Seogjae; Shin, Haijin; Sarwade, Bhimrao D; Na, Jongbeom; Kim, Eunkyoung

2015-01-01

An electrochemically stable and bistable switchable mirror was achieved for the first time by introducing (1) a thiol-modified indium tin oxide (ITO) electrode for the stabilization of the metallic film and (2) ionic liquids as an anion-blocking layer, to achieve a long memory effect. The growth of the metallic film was denser and faster at the thiol-modified ITO electrode than at a bare ITO electrode. The electrochemical stability of the metallic film on the thiol-modified ITO was enhanced, maintaining the metallic state without rupture. In the voltage-off state, the metal film maintained bistability for a long period (>2 h) when ionic liquids were introduced as electrolytes for the switchable mirror. The electrical double layer in the highly viscous ionic liquid electrolyte seemed to effectively form a barrier to the bromide ions, to protect the metal thin film from them when in the voltage-off state.

Electrodeposition of platinum and silver into chemically modified microporous silicon electrodes

PubMed Central

2012-01-01

Electrodeposition of platinum and silver into hydrophobic and hydrophilic microporous silicon layers was investigated using chemically modified microporous silicon electrodes. Hydrophobic microporous silicon enhanced the electrodeposition of platinum in the porous layer. Meanwhile, hydrophilic one showed that platinum was hardly deposited within the porous layer, and a film of platinum on the top of the porous layer was observed. On the other hand, the electrodeposition of silver showed similar deposition behavior between these two chemically modified electrodes. It was also found that the electrodeposition of silver started at the pore opening and grew toward the pore bottom, while a uniform deposition from the pore bottom was observed in platinum electrodeposition. These electrodeposition behaviors are explained on the basis of the both effects, the difference in overpotential for metal deposition on silicon and on the deposited metal, and displacement deposition rate of metal. PMID:22720690

Integrated multidimensional and comprehensive 2D GC analysis of fatty acid methyl esters.

PubMed

Zeng, Annie Xu; Chin, Sung-Tong; Marriott, Philip J

2013-03-01

Fatty acid methyl ester (FAME) profiling in complex fish oil and milk fat samples was studied using integrated comprehensive 2D GC (GC × GC) and multidimensional GC (MDGC). Using GC × GC, FAME compounds--cis- and trans-isomers, and essential fatty acid isomers--ranging from C18 to C22 in fish oil and C18 in milk fat were clearly displayed in contour plot format according to structural properties and patterns, further identified based on authentic standards. Incompletely resolved regions were subjected to MDGC, with Cn (n = 18, 20) zones transferred to a (2)D column. Elution behavior of C18 FAME on various (2)D column phases (ionic liquids IL111, IL100, IL76, and modified PEG) was evaluated. Individual isolated Cn zones demonstrated about four-fold increased peak capacities. The IL100 provided superior separation, good peak shape, and utilization of elution space. For milk fat-derived FAME, the (2)D chromatogram revealed at least three peaks corresponding to C18:1, more than six peaks for cis/trans-C18:2 isomers, and two peaks for C18:3. More than 17 peaks were obtained for the C20 region of fish oil-derived FAMEs using MDGC, compared with ten peaks using GC × GC. The MDGC strategy is useful for improved FAME isomer separation and confirmation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular modification of highly degenerate semiconductor as an active electrode to enhance the performance of supercapacitors

NASA Astrophysics Data System (ADS)

Mundinamani, S. P.; Rabinal, M. K.

2014-12-01

Highly conducting antimony doped tin oxide (SnO2:Sb) films are electrografted with suitable organic molecules to study their electrolytic behavior. A series of organic molecules, such as heptanethiol, dodecanethiol and octadecanethiol are bonded to electrode surfaces. Electrolytic capacitors were formed on both unmodified and chemically modified electrodes using KCl and H2SO4 as electrolytes. This molecular modification significantly enhances the current levels in cyclic voltammograms, and there is a clear shift in oxidation/reduction peaks of these capacitors with scan rate. The results obey Randles-Sevcik relation, which indicates that there is enhancement of ionic diffusion at the electrode-electrolyte interface. There is a large enhancement in the values of specific capacitance (almost by 104 times) after the chemical modification. These measurements show that Faradaic reactions are responsible for charge storage/discharge process in these capacitors. Hence, the molecularly modified electrodes can be a good choice to increase the specific capacitance.

Construction of ferrocene modified conducting polymer based amperometric urea biosensor.

PubMed

Dervisevic, Muamer; Dervisevic, Esma; Senel, Mehmet; Cevik, Emre; Yildiz, Huseyin Bekir; Camurlu, Pınar

2017-07-01

Herein, an electrochemical urea sensing bio-electrode is reported that has been constructed by firstly electropolymerizing 4-(2,5-Di(thiophen-2-yl)-1H-pyrrol-1-yl)aniline monomer (SNS-Aniline) on Pencil Graphite Electrode (PGE), then modifying the polymer coated electrode surface with di-amino-Ferrocene (DAFc) as the mediator, and lastly Urease enzyme through glutaraldehyde crosslinking. The effect of pH, temperature, polymer thickness, and applied potential on the electrode current response was investigated besides performing storage and operational stability experiments with the interference studies. The resulting urea biosensor's amperometric response was linear in the range of 0.1-8.5mM with the sensitivity of 0.54μA/mM, detection limit of 12μM, and short response time of 2s. The designed bio-electrode was tested with real human blood and urine samples where it showed excellent analytical performance with insignificant interference. Copyright © 2017 Elsevier Inc. All rights reserved.

Determination of glutamine and glutamic acid in mammalian cell cultures using tetrathiafulvalene modified enzyme electrodes.

PubMed

Mulchandani, A; Bassi, A S

1996-01-01

Tetrathiafulvalene (TTF) mediated amperometric enzyme electrodes have been developed for the monitoring of L-glutamine and L-glutamic acid in growing mammalian cell cultures. The detection of glutamine was accomplished by a coupled enzyme system comprised of glutaminase plus glutamate oxidase, while the detection of glutamic acid was carried out by a single enzyme, glutamate oxidase. The appropriate enzyme(s) were immoblized on the Triton-X treated surface of tetrathiafulvalene modified carbon paste electrodes by adsorption, in conjunction with entrapment by an electrochemically deposited copolymer film of 1,3-phenylenediamine and resorcinol. Operating conditions for the glutamine enzyme electrode were optimized with respect to the amount of enzymes immoblized, pH, temperature and mobile phase flow rate for operation in a flow injection (FIA) system. When applied to glutamine and glutamic acid measurements in mammalian cell culture in FIA, the results obtained with enzyme electrodes were in excellent agreement with those determined by enzymatic analysis.

Perovskite LaTiO₃-Ag0.2 nanomaterials for nonenzymatic glucose sensor with high performance.

PubMed

Wang, Yin-zhu; Zhong, Hui; Li, Xiao-mo; Jia, Fei-fei; Shi, Yi-xiang; Zhang, Wei-guang; Cheng, Zhi-peng; Zhang, Li-li; Wang, Ji-kui

2013-10-15

In this paper, a nonenzymatic glucose biosensor based on perovskite LaTiO3-Ag0.2(LTA) modified electrode was presented. The morphology and the composition of the perovskite LaTiO₃-Ag0.2 nanomaterials were characterized by using scanning electron microscopy (SEM) and X-ray diffraction (XRD) respectively. The LaTiO₃-Ag0.2(LTA) composite was investigated by electrochemical characterization using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Under optimal conditions, CV and chronoamperometry (I-t) study revealed that, compared with the bare glassy carbon electrode (GCE), the modified electrode showed a remarkable increase in the efficiency of the electrocatalytic oxidation of glucose, starting at around +0.70 V (vs. Ag/AgCl). The prepared sensor exhibited a high sensitivity of 784.14 µAmM⁻¹ cm⁻², a low detection limit of 2.1×10⁻⁷ M and a wide linear range from 2.5 µM to 4 mM (R=0.9997). More importantly, the LTA modified electrode was also relatively insensitive to commonly interfering species such as ascorbic acid (AA), uric acid (UA), dopamine (DA) in high potential. Moreover, the nonenzymatic sensor was applied to the determination of glucose in human serum samples and the results were in good agreement with clinical data. Electrodes modified with perovskite nanomaterials are highly promising for nonenzymatic electrochemical detection of glucose because of their high sensitivity, fast response, excellent stability and good reproducibility. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrode Modification and Optimization in Air-Cathode Single-Chamber Microbial Fuel Cells.

PubMed

Wang, Yanhua; Wu, Jiayan; Yang, Shengke; Li, Huihui; Li, Xiaoping

2018-06-27

Due to the known problems of microbial fuel cells (MFCs), such as low electricity generation performance and high cost of operation, we modified the electrode with graphene and polyaniline (PANI) is a single-chamber air-cathode MFC and then evaluated the effects of electrode modification on MFC electricity generation performance. Carbon cloth electrodes (unmodified, CC; graphene-modified, G/CC; and polyaniline-graphene-modified, PANI-G/CC) were prepared using the impregnation method. Sulfonated cobalt phthalocyanine (CoPcS) was then introduced as a cathode catalyst. The Co-PANI-G/CC cathode showed higher catalytic activity toward oxygen reduction compared with other electrodes. The maximum power density of the MFC with Co-PANI-G/CC cathode was 32.2 mW/m², which was 1.8 and 6.1 times higher than the value obtained with Co-G/CC and Co/CC cathodes, respectively. This indicates a significant improvement in the electricity generation of single-chamber MFCs and provides a simple, effective cathode modification method. Furthermore, we constructed single-chamber MFCs using the modified anode and cathode and analyzed electricity generation and oxytetracycline (OTC) degradation with different concentrations of OTC as the fuel. With increasing added OTC concentration, the MFC performance in both electricity generation and OTC degradation gradually decreased. However, when less than 50 mg/L OTC was added, the 5-day degradation rate of OTC reached more than 90%. It is thus feasible to process OTC-containing wastewater and produce electricity using single-chamber MFCs, which provides a new concept for wastewater treatment.

Combination of cathodic reduction with adsorption for accelerated removal of Cr(VI) through reticulated vitreous carbon electrodes modified with sulfuric acid-glycine co-doped polyaniline.

PubMed

Mo, Xi; Yang, Zhao-hui; Xu, Hai-yin; Zeng, Guang-ming; Huang, Jing; Yang, Xia; Song, Pei-pei; Wang, Li-ke

2015-04-09

Improving the reduction kinetics is crucial in the electroreduction process of Cr(VI). In this study, we developed a novel adsorption-electroreduction system for accelerated removal of Cr(VI) by employing reticulated vitreous carbon electrode modified with sulfuric acid-glycine co-doped polyaniline (RVC/PANI-SA-GLY). Firstly, response surface methodology confirmed the optimum polymerization condition of co-doped polyaniline for modifying electrodes (Aniline, sulfuric acid and glycine, respectively, of 0.2 mol/L, 0.85 mol/L, 0.93 mol/L) when untraditional dopant glycine was added. Subsequently, RVC/PANI-SA-GLY showed higher Cr(VI) removal percentages in electroreduction experiments over RVC electrode modified with sulfuric acid doped polyaniline (RVC/PANI-SA) and bare RVC electrode. In contrast to RVC/PANI-SA, the improvement by RVC/PANI-SA-GLY was more significant and especially obvious at more negative potential, lower initial Cr(VI) concentration, relatively less acidic solution and higher current densities, best achieving 7.84% higher removal efficiency with entire Cr(VI) eliminated after 900 s. Current efficiencies were likewise enhanced by RVC/PANI-SA-GLY under quite negative potentials. Fourier transform infrared (FTIR) and energy dispersive spectrometer (EDS) analysis revealed a possible adsorption-reduction mechanism of RVC/PANI-SA-GLY, which greatly contributed to the faster reduction kinetics and was probably relative to the absorption between protonated amine groups of glycine and HCrO4(-). Eventually, the stability of RVC/PANI-SA-GLY was proven relatively satisfactory. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrocatalytic activity of cobalt phosphide-modified graphite felt toward VO2+/VO2+ redox reaction

NASA Astrophysics Data System (ADS)

Ge, Zhijun; Wang, Ling; He, Zhangxing; Li, Yuehua; Jiang, Yingqiao; Meng, Wei; Dai, Lei

2018-04-01

A novel strategy for improving the electro-catalytic properties of graphite felt (GF) electrode in vanadium redox flow battery (VRFB) is designed by depositing cobalt phosphide (CoP) onto GF surface. The CoP powder is synthesized by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) followed by phosphidation. Cyclic voltammetry results confirm that the CoP-modified graphite felt (GF-CoP) electrode has excellent reversibility and electro-catalytic activity to the VO2+/VO2+ cathodic reaction compared with the pristine GF electrode. The cell using GF-CoP electrode shows apparently higher discharge capacity over that based on GF electrode. The cell using GF-CoP electrode has the capacity of 67.2 mA h at 100 mA cm-2, 32.7 mA h larger than that using GF electrode. Compared with cell using GF electrode, the voltage efficiency of the cell based on GF-CoP electrode increases by 5.9% and energy efficiency by 5.4% at a current density of 100 mA cm-2. The cell using GF-CoP electrode can reach 94.31% capacity retention after 50 cycles at a current density of 30 mA cm-2. The results show that the CoP can effectively promote the VO2+/VO2+ redox reaction, implying that metal phosphides are a new kind of potential catalytic materials for VRFB.

Headspace Analysis of Ammonium Nitrate

DTIC Science & Technology

2017-01-25

to an Agilent 7890 gas chromatograph (GC) (Agilent Technologies, Santa Clara, CA). Methane CI was used to optimize instrument parameters, which...order of 0.1 mTorr, as were CF2Cl2, CF3Cl, methane , and isobutane. Figure 2. Analyte sorbent tube mounted and interfaced with a modified GC...observed at no more than 22% abundance of m/z 17. When larger gases such as methane were mixed in significant proportion with 500 ppm carbon

Study of the Electrocatalytic Activity of Cerium Oxide and Gold-Studded Cerium Oxide Nanoparticles Using a Sonogel-Carbon Material as Supporting Electrode: Electroanalytical Study in Apple Juice for Babies

PubMed Central

Abdelrahim, M. Yahia M.; Benjamin, Stephen R.; Cubillana-Aguilera, Laura Ma; Naranjo-Rodríguez, Ignacio; Hidalgo-Hidalgo de Cisneros, Josè L.; Delgado, Juan Josè; Palacios-Santander, Josè Ma

2013-01-01

The present work reports a study of the electrocatalytic activity of CeO2 nanoparticles and gold sononanoparticles (AuSNPs)/CeO2 nanocomposite, deposited on the surface of a Sonogel-Carbon (SNGC) matrix used as supporting electrode and the application of the sensing devices built with them to the determination of ascorbic acid (AA) used as a benchmark analyte. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to investigate the electrocatalytic behavior of CeO2- and AuSNPs/CeO2-modified SNGC electrodes, utilizing different concentrations of CeO2 nanoparticles and different AuSNPs:CeO2 w/w ratios. The best detection and quantification limits, obtained for CeO2 (10.0 mg·mL−1)- and AuSNPs/CeO2 (3.25% w/w)-modified SNGC electrodes, were 1.59 × 10−6 and 5.32 × 10−6 M, and 2.93 × 10−6 and 9.77 × 10−6 M, respectively, with reproducibility values of 5.78% and 6.24%, respectively, for a linear concentration range from 1.5 μM to 4.0 mM of AA. The electrochemical devices were tested for the determination of AA in commercial apple juice for babies. The results were compared with those obtained by applying high performance liquid chromatography (HPLC) as a reference method. Recovery errors below 5% were obtained in most cases, with standard deviations lower than 3% for all the modified SNGC electrodes. Bare, CeO2- and AuSNPs/CeO2-modified SNGC electrodes were structurally characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). AuSNPs and AuSNPs/CeO2 nanocomposite were characterized by UV-vis spectroscopy and X-ray diffraction (XRD), and information about their size distribution and shape was obtained by transmission electron microscopy (TEM;. The advantages of employing CeO2 nanoparticles and AuSNPs/CeO2 nanocomposite in SNGC supporting material are also described. This research suggests that the modified electrode can be a very promising voltammetric sensor for the determination of electroactive species of interest in real samples. PMID:23584124

Study of the electrocatalytic activity of cerium oxide and gold-studded cerium oxide nanoparticles using a Sonogel-Carbon material as supporting electrode: electroanalytical study in apple juice for babies.

PubMed

Abdelrahim, M Yahia M; Benjamin, Stephen R; Cubillana-Aguilera, Laura Ma; Naranjo-Rodríguez, Ignacio; de Cisneros, José L Hidalgo-Hidalgo; Delgado, Juan José; Palacios-Santander, José Ma

2013-04-12

The present work reports a study of the electrocatalytic activity of CeO2 nanoparticles and gold sononanoparticles (AuSNPs)/CeO2 nanocomposite, deposited on the surface of a Sonogel-Carbon (SNGC) matrix used as supporting electrode and the application of the sensing devices built with them to the determination of ascorbic acid (AA) used as a benchmark analyte. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to investigate the electrocatalytic behavior of CeO2- and AuSNPs/CeO2-modified SNGC electrodes, utilizing different concentrations of CeO2 nanoparticles and different AuSNPs:CeO2 w/w ratios. The best detection and quantification limits, obtained for CeO2 (10.0 mg·mL(-1))- and AuSNPs/CeO2 (3.25% w/w)-modified SNGC electrodes, were 1.59 × 10(-6) and 5.32 × 10(-6) M, and 2.93 × 10(-6) and 9.77 × 10(-6) M, respectively, with reproducibility values of 5.78% and 6.24%, respectively, for a linear concentration range from 1.5 µM to 4.0 mM of AA. The electrochemical devices were tested for the determination of AA in commercial apple juice for babies. The results were compared with those obtained by applying high performance liquid chromatography (HPLC) as a reference method. Recovery errors below 5% were obtained in most cases, with standard deviations lower than 3% for all the modified SNGC electrodes. Bare, CeO2- and AuSNPs/CeO2-modified SNGC electrodes were structurally characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). AuSNPs and AuSNPs/CeO2 nanocomposite were characterized by UV-vis spectroscopy and X-ray diffraction (XRD), and information about their size distribution and shape was obtained by transmission electron microscopy (TEM). The advantages of employing CeO2 nanoparticles and AuSNPs/CeO2 nanocomposite in SNGC supporting material are also described. This research suggests that the modified electrode can be a very promising voltammetric sensor for the determination of electroactive species of interest in real samples.

Synthesis of three-dimensional mesoporous Cu-Al layered double hydroxide/g-C3N4 nanocomposites on Ni-foam for enhanced supercapacitors with excellent long-term cycling stability.

PubMed

Adhikari, Surya Prasad; Awasthi, Ganesh Prasad; Kim, Kyung-Suk; Park, Chan Hee; Kim, Cheol Sang

2018-03-26

In this study, a novel composite of Cu-Al layered double hydroxide (LDH) nanosheets and g-C3N4-covered Ni-foam was fabricated via a simple and facile two-step process. First, g-C3N4 sheets were deposited on Ni-foam by via electrodeposition method on a three-electrode system (Ni-foam@g-C3N4) and then, Cu-Al LDH nanosheets were grown on the Ni-foam via in situ redox reaction using a hydrothermal process (Ni-foam@Cu-Al LDH/g-C3N4). The FE-SEM image confirmed that the Cu-Al LDH nanosheets arose vertically and were anchored on the surface of electrodeposited g-C3N4 sheets, thus generating unique 3D porous interconnected networks. The electrochemical capacitive performances of the as-prepared samples were evaluated by cyclic volatammetry (CV), galvanostatic charge/discharge tests, and electrochemical impedance spectra (EIS) Nyquist plots. The specific capacitances of the Ni-foam@Cu-Al LDH/g-C3N4 nanocomposite measured from the CV curve (770.98 F g-1 at 50 mV s-1) and the galvanostatic charge/discharge curve (831.871 at 0.4 A g-1) were significantly higher than the others. Moreover, the Ni-foam@Cu-Al LDH/g-C3N4 nanocomposite revealed a remarkable high-current capacitive behavior and the capacitance retention could be maintained at 92.71% even after 5000 cycles of CV. Thus, the obtained results demonstrated that the as-prepared nanocomposite has great potential to be used as a novel supercapacitor electrode.

Block Copolymer Patterns as Templates for the Electrocatalyzed Deposition of Nanostructures on Electrodes and for the Generation of Surfaces of Controlled Wettability.

PubMed

Chandaluri, Chanchayya Gupta; Pelossof, Gilad; Tel-Vered, Ran; Shenhar, Roy; Willner, Itamar

2016-01-20

ITO electrodes modified with a nanopatterned film of polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP, where the P2VP domains are quaternized with iodomethane, are used for selective deposition of redox-active materials. Electrochemical studies (cyclic voltammetry, Faradaic impedance measurements) indicate that the PS domains insulate the conductive surface toward redox labels in solution. In turn, the quaternized P2VP domains electrostatically attract negatively charged redox labels solubilized in the electrolyte solution, resulting in an effective electron transfer between the electrode and the redox label. This phenomenon is implemented for the selective deposition of the electroactive Prussian blue on the nanopatterned surface and for the electrochemical deposition of Au nanoparticles, modified with a monolayer of p-aminothiophenol/2-mercaptoethanesulfonic acid, on the quaternized P2VP domains. The patterned Prussian blue-modified surface enables controlling the wettability properties by the content of the electrochemically deposited Prussian blue. Controlled wettability is unattainable with the homopolymer-modified surface, attesting to the role of the nanopattern.

Dispersion of bamboo type multi-wall carbon nanotubes in calf-thymus double stranded DNA.

PubMed

Primo, Emiliano N; Cañete-Rosales, Paulina; Bollo, Soledad; Rubianes, María D; Rivas, Gustavo A

2013-08-01

We report for the first time the use of double stranded calf-thymus DNA (dsDNA) to successfully disperse bamboo-like multi-walled carbon nanotubes (bCNT). The dispersion and the modified electrodes were studied by different spectroscopic, microscopic and electrochemical techniques. The drastic treatment for dispersing the bCNT (45min sonication in a 50% (v/v) ethanol:water solution), produces a partial denaturation and a decrease in the length of dsDNA that facilitates the dispersion of CNT and makes possible an efficient electron transfer of guanine residues to the electrode. A critical analysis of the influence of different experimental conditions on the efficiency of the dispersion and on the performance of glassy carbon electrodes (GCE) modified with bCNT-dsDNA dispersion is also reported. The electron transfer of redox probes and guanine residues was more efficient at GCE modified with bCNT dispersed in dsDNA than at GCE modified with hollow CNT (hCNT) dispersed in dsDNA, demonstrating the importance of the presence of bCNT. Copyright © 2013 Elsevier B.V. All rights reserved.

A polyamidoamine dendrimer-streptavidin supramolecular architecture for biosensor development.

PubMed

Soda, N; Arotiba, O A

2017-12-01

A novel polyamidoamine dendrimer-streptavidin supramolecular architecture suitable as a versatile platform for biosensor development is reported. The dendrimer was electrodeposited on a glassy carbon electrode via cyclic voltammetry. The dendrimer electrode was further modified with streptavidin by electrostatic attraction upon drop coating. The platform i.e. the dendrimer-streptavidin modified electrode was electrochemically interrogated in phosphate buffer, ferrocyanide and H 2 O 2 . The dendrimer-streptavidin platform was used in the preparation of a simple DNA biosensor as a proof of concept. The supramolecular architecture of dendrimer-streptavidin was stable, electroactive and thus lends itself as a versatile immobilisation layer for any biotinylated bioreceptors in biosensor development. Copyright © 2017 Elsevier B.V. All rights reserved.

Anchor of Ni2+ on the Agmatine Sulfate-Modified Electrodes for the Determination of H2O2 in Food

NASA Astrophysics Data System (ADS)

Yan, Yuhua; Zhang, Zhonghui; Xiao, Mingshu; Zhou, Hualan

2017-07-01

A method was developed to conveniently and rapidly determine hydrogen peroxide (H2O2) in food. The glassy carbon electrode (GCE) modified with agmatine sulfate (AS) easily anchoring nickel ion was attached to AS with polyamine structure. As a result, more Ni2+ was obtained and transformed to Ni(OH)2/NiOOH on the AS-GCE, which caused the electrode to own much better electrocatalytic performance on H2O2. Based on these, the content of H2O2 in thin sheet of bean curd sample was detected with standard addition method, by which good results were obtained.

An all-solid-state lithium/polyaniline rechargeable cell

NASA Astrophysics Data System (ADS)

Li, Changzhi; Peng, Xinsheng; Zhang, Borong; Wang, Baochen

1992-07-01

The performance of an all-solid-state cell having a lithium negative electrode, a modified polyethylene oxide (PEO)-epoxy resin (ER) electrolyte, and a polyaniline (PAn) positive electrode has been studied using cyclic voltammetry, charge/discharge cycling, and polarization curves at various temperatures. The redox reaction of the PAn electrode at the PAn/modified PEO-ER interface exhibits good reversibility. At 50-80 C, the Li/PEO-ER-LiClO4/PAn cell shows more than 40 charge/discharge cycles, 90 percent charge/discharge efficiency, and 54 W h kg discharge energy density (on PAn weight basis) at 50 micro-A between 2 and 4 V. The polarization performance of the battery improves steadily with increase in temperature.

Interlayer shear behaviors of graphene-carbon nanotube network

NASA Astrophysics Data System (ADS)

Qin, Huasong; Liu, Yilun

2017-09-01

The interlayer shear resistance plays an important role in graphene related applications, and different mechanisms have been proposed to enhance its interlayer load capacity. In this work, we performed molecular dynamics (MD) simulations and theoretical analysis to study interlayer shear behaviors of three dimensional graphene-carbon (3D-GC) nanotube networks. The shear mechanical properties of carbon nanotubes (CNTs) crosslink with different diameters are obtained which is one order of magnitude larger than that of other types of crosslinks. Under shear loading, 3D-GC exhibits two failure modes, i.e., fracture of graphene sheet and failure of CNT crosslink, determined by the diameter of CNT crosslink, crosslink density, and length of 3D-GC. A modified tension-shear chain model is proposed to predict the shear mechanical properties and failure mode of 3D-GC, which agrees well with MD simulation results. The results presented in this work may provide useful insights for future development of high-performance 3D-GC materials.

Cu-modified alkalinized g-C3N4 as photocatalytically assisted heterogeneous Fenton-like catalyst

NASA Astrophysics Data System (ADS)

Dong, Qimei; Chen, Yingying; Wang, Lingli; Ai, Shasha; Ding, Hanming

2017-12-01

Alkalinized graphitic carbon nitride (CNK-OH) has been synthesized by one-step thermal poly-condensation method, and Cu-modified alkalinized g-C3N4 (Cu-CNK-OH) has been prepared by impregnation approach over CNK-OH. These copper species in Cu-CNK-OH are embedded in the frame of CNK-OH mostly via the Cu-N bonds. Cu-CNK-OH has been employed as a heterogeneous Fenton-like catalyst to degrade rhodamine B (RhB). Both the production efficiency of hydroxyl radicals and the transformation rate of Cu(II)/Cu(I) redox pair increase under visible-light irradiation. As a result, Cu-CNK-OH exhibits improved Fenton-like catalytic activity on the degradation of RhB. The synergetic interaction between Fenton-like process and photocatalytic process also contributes such improvement. The hydroxyl radicals and holes are the major reactive species in the photocatalytically assisted Fenton-like process. This study provides a valuable strategy for metal modification of alkalinized g-C3N4 with enhanced Fenton-like catalytic performance for the degradation of organic contaminants.

Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

DOEpatents

Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

2010-03-02

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

DOEpatents

Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

2010-11-23

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

Pencil graphite electrodes for improved electrochemical detection of oleuropein by the combination of Natural Deep Eutectic Solvents and graphene oxide.

PubMed

Gomez, Federico J V; Spisso, Adrian; Fernanda Silva, María

2017-11-01

A novel methodology is presented for the enhanced electrochemical detection of oleuropein in complex plant matrices by Graphene Oxide Pencil Grahite Electrode (GOPGE) in combination with a buffer modified with a Natural Deep Eutectic Solvent, containing 10% (v/v) of Lactic acid, Glucose and H 2 O (LGH). The electrochemical behavior of oleuropein in the modified-working buffer was examined using differential pulse voltammetry. The combination of both modifications, NADES modified buffer and nanomaterial modified electrode, LGH-GOPGE, resulted on a signal enhancement of 5.3 times higher than the bare electrode with unmodified buffer. A calibration curve of oleuropein was performed between 0.10 to 37 μM and a good linearity was obtained with a correlation coefficient of 0.989. Detection and quantification limits of the method were obtained as 30 and 102 nM, respectively. In addition, precision studies indicated that the voltammetric method was sufficiently repeatable, %RSD 0.01 and 3.16 (n = 5) for potential and intensity, respectively. Finally, the proposed electrochemical sensor was successfully applied to the determination of oleuropein in an olive leaf extract prepared by ultrasound-assisted extraction. The results obtained with the proposed electrochemical sensor were compared with Capillary Zone Electrophoresis analysis with satisfactory results. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene frameworks synthetized with Na2CO3 as a renewable water-soluble substrate and their high rate capability for supercapacitors

NASA Astrophysics Data System (ADS)

Cui, Huijuan; Zheng, Jianfeng; Zhu, Yanyan; Wang, Zhijian; Jia, Suping; Zhu, Zhenping

2015-10-01

Substrates are normally required in the chemical synthesis of graphene to enhance its formation. However, removing substrates in the post purification stage is difficult, during which harsh reagents are used and the substrates are usually consumed undesirably. In this paper, we report that universal sodium carbonate (Na2CO3) particles can effectively promote the construction of well-structured graphene frameworks based on a quick thermal decomposition of fumaric acids. Notably, the Na2CO3 particles are easily separated from graphene through a simple and green method, namely, washing with water at room temperature. Together with the reused characteristic of the recovered Na2CO3 particles, this approach is undoubtedly beneficial to the low-cost and clean synthesis of graphene. Benefiting from the framework structure, the as-synthesized graphene exhibits excellent performance in the supercapacitor. The specific capacitance of the GFs-modified electrode was calculated to be 242 F g-1 at 0.5 A g-1, which was almost twice that of the RGO-modified electrode (134 F g-1). More importantly, the GFs-modified electrode maintained 92.6% retention of its initial specific capacitance (from current density of 0.5 to 16 A g-1), which was much higher than that of 2D graphene-modified electrode.

para-Sulfonatocalix[6]arene-modified silver nanoparticles electrodeposited on glassy carbon electrode: preparation and electrochemical sensing of methyl parathion.

PubMed

Bian, Yinghui; Li, Chunya; Li, Haibing

2010-05-15

In this paper, a new electrochemical sensor, based on modified silver nanoparticles, was fabricated using one-step electrodeposition approach. The para-sulfonatocalix[6]arene-modified silver nanoparticles coated on glassy carbon electrode (pSC(6)-Ag NPs/GCE) was characterized by attenuated total reflection IR spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), etc. The pSC(6) as the host are highly efficient to capture organophosphates (OPs), which dramatically facilitates the enrichment of nitroaromatic OPs onto the electrochemical sensor surface. The combination of the host-guest supramolecular structure and the excellent electrochemical catalytic activities of the pSC(6)-Ag NPs/GCE provides a fast, simple, and sensitive electrochemical method for detecting nitroaromatic OPs. In this work, methyl parathion (MP) was used as a nitroaromatic OP model for testing the proposed sensor. In comparison with Ag NPs-modified electrode, the cathodic peak current of MP was amplified significantly. Differential pulse voltammetry was used for the simultaneous determination of MP. Under optimum conditions, the current increased linearly with the increasing concentration of MP in the range of 0.01-80microM, with a detection limit of 4.0nM (S/N=3). The fabrication reproducibility and stability of the sensor is better than that of enzyme-based electrodes. The possible underlying mechanism is discussed.

Effect of Binder Architecture on the Performance of Silicon/Graphite Composite Anodes for Lithium Ion Batteries

DOE PAGES

Cao, Peng-Fei; Naguib, Michael; Du, Zhijia; ...

2018-01-04

Although significant progress has been made in improving cycling performance of silicon-based electrodes, few studies have been performed on the architecture effect on polymer binder performance for lithium-ion batteries. A systematic study on the relationship between polymer architectures and binder performance is especially useful in designing synthetic polymer binders. In this paper, a graft block copolymer with readily tunable architecture parameters is synthesized and tested as the polymer binder for the high-mass loading silicon (15 wt %)/graphite (73 wt %) composite electrode (active materials >2.5 mg/cm 2). With the same chemical composition and functional group ratio, the graft block copolymermore » reveals improved cycling performance in both capacity retention (495 mAh/g vs 356 mAh/g at 100th cycle) and Coulombic efficiency (90.3% vs 88.1% at first cycle) than the physical mixing of glycol chitosan (GC) and lithium polyacrylate (LiPAA). Galvanostatic results also demonstrate the significant impacts of different architecture parameters of graft copolymers, including grafting density and side chain length, on their ultimate binder performance. Finally, by simply changing the side chain length of GC-g-LiPAA, the retaining delithiation capacity after 100 cycles varies from 347 mAh/g to 495 mAh/g.« less

Effect of Binder Architecture on the Performance of Silicon/Graphite Composite Anodes for Lithium Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Peng-Fei; Naguib, Michael; Du, Zhijia

Although significant progress has been made in improving cycling performance of silicon-based electrodes, few studies have been performed on the architecture effect on polymer binder performance for lithium-ion batteries. A systematic study on the relationship between polymer architectures and binder performance is especially useful in designing synthetic polymer binders. In this paper, a graft block copolymer with readily tunable architecture parameters is synthesized and tested as the polymer binder for the high-mass loading silicon (15 wt %)/graphite (73 wt %) composite electrode (active materials >2.5 mg/cm 2). With the same chemical composition and functional group ratio, the graft block copolymermore » reveals improved cycling performance in both capacity retention (495 mAh/g vs 356 mAh/g at 100th cycle) and Coulombic efficiency (90.3% vs 88.1% at first cycle) than the physical mixing of glycol chitosan (GC) and lithium polyacrylate (LiPAA). Galvanostatic results also demonstrate the significant impacts of different architecture parameters of graft copolymers, including grafting density and side chain length, on their ultimate binder performance. Finally, by simply changing the side chain length of GC-g-LiPAA, the retaining delithiation capacity after 100 cycles varies from 347 mAh/g to 495 mAh/g.« less

Functionalized Graphitic Carbon Nitride for Metal-free, Flexible and Rewritable Nonvolatile Memory Device via Direct Laser-Writing

NASA Astrophysics Data System (ADS)

Zhao, Fei; Cheng, Huhu; Hu, Yue; Song, Long; Zhang, Zhipan; Jiang, Lan; Qu, Liangti

2014-07-01

Graphitic carbon nitride nanosheet (g-C3N4-NS) has layered structure similar with graphene nanosheet and presents unusual physicochemical properties due to the s-triazine fragments. But their electronic and electrochemical applications are limited by the relatively poor conductivity. The current work provides the first example that atomically thick g-C3N4-NSs are the ideal candidate as the active insulator layer with tunable conductivity for achieving the high performance memory devices with electrical bistability. Unlike in conventional memory diodes, the g-C3N4-NSs based devices combined with graphene layer electrodes are flexible, metal-free and low cost. The functionalized g-C3N4-NSs exhibit desirable dispersibility and dielectricity which support the all-solution fabrication and high performance of the memory diodes. Moreover, the flexible memory diodes are conveniently fabricated through the fast laser writing process on graphene oxide/g-C3N4-NSs/graphene oxide thin film. The obtained devices not only have the nonvolatile electrical bistability with great retention and endurance, but also show the rewritable memory effect with a reliable ON/OFF ratio of up to 105, which is the highest among all the metal-free flexible memory diodes reported so far, and even higher than those of metal-containing devices.

Bromination of aromatic compounds by residual bromide in sodium chloride matrix modifier salt during heated headspace GC/MS analysis.

PubMed

Fine, Dennis D; Ko, Saebom; Huling, Scott

2013-12-15

Analytical artifacts attributed to the bromination of toluene, xylenes, and trimethylbenzenes were found during the heated headspace gas chromatography/mass spectrometry (GC/MS) analysis of aqueous samples. The aqueous samples were produced from Fenton-like chemical oxidation reactions and contained aromatic compounds, hydrogen peroxide (H2O2), and ferric sulfate. Prior to GC/MS headspace analysis, the samples were acidified (pH<2), and sodium chloride was amended to the headspace vial as a matrix modifier. The brominated artifacts were generated during heated headspace analysis. Further, when samples were spiked with a mixture of volatile chlorinated and aromatic compounds (50 µg/L), poor spike recoveries of toluene and xylenes occurred, and in some cases complete loss of trimethylbenzenes and naphthalene resulted. Where poor recovery of aromatic spike compounds occurred, brominated aromatic compounds were found. The only significant source of bromine in the reaction scheme is the bromide typically present (<0.01% w/w) in the sodium chloride amended to the samples. Conversely, brominated artifacts were absent when a buffered salt mixture composed of sodium chloride and potassium phosphate dibasic/monobasic was used as a matrix modifier and raised the sample pH (pH~6). This indicated that the brominated artifacts resulted from the reaction of the aromatic compounds with BrCl, which was formed by the reaction of H2O2, chloride, and bromide under acidic conditions. An alternative matrix modifier salt is recommended that prevents the bromination reaction and avoids these deleterious effects on sample integrity during headspace analysis. Published by Elsevier B.V.

Direct Measurement of Cyclic Current-Voltage Responses of Integral Membrane Proteins at a Self-Assembled Lipid-Bilayer-Modified Electrode: Cytochrome f and Cytochrome c Oxidase

NASA Astrophysics Data System (ADS)

Salamon, Z.; Hazzard, J. T.; Tollin, G.

1993-07-01

Direct cyclic voltage-current responses, produced in the absence of redox mediators, for two detergent-solubilized integral membrane proteins, spinach cytochrome f and beef heart cytochrome c oxidase, have been obtained at an optically transparent indium oxide electrode modified with a self-assembled lipid-bilayer membrane. The results indicate that both proteins interact with the lipid membrane so as to support quasi-reversible electron transfer redox reactions at the semiconductor electrode. The redox potentials that were obtained from analysis of the cyclic "voltammograms," 365 mV for cytochrome f and 250 and 380 mV for cytochrome c oxidase (vs. normal hydrogen electrode), compare quite well with the values reported by using conventional titration methods. The ability to obtain direct electrochemical measurements opens up another approach to the investigation of the properties of integral membrane redox proteins.

Graphite felt modified with bismuth nanoparticles as negative electrode in a vanadium redox flow battery.

PubMed

Suárez, David J; González, Zoraida; Blanco, Clara; Granda, Marcos; Menéndez, Rosa; Santamaría, Ricardo

2014-03-01

A graphite felt decorated with bismuth nanoparticles was studied as negative electrode in a vanadium redox flow battery (VRFB). The results confirm the excellent electrochemical performance of the bismuth modified electrode in terms of the reversibility of the V(3+) /V(2+) redox reactions and its long-term cycling performance. Moreover a mechanism that explains the role that Bi nanoparticles play in the redox reactions in this negative half-cell is proposed. Bi nanoparticles favor the formation of BiHx , an intermediate that reduces V(3+) to V(2+) and, therefore, inhibits the competitive irreversible reaction of hydrogen formation (responsible for the commonly observed loss of Coulombic efficiency of VRFBs). Thus, the total charge consumed during the cathodic sweep in this electrode is used to reduce V(3+) to V(2+) , resulting in a highly reversible and efficient process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Glucose biosensing using glassy carbon electrode modified with polyhydroxy-C60, glucose oxidase and ionic-liquid.

PubMed

Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, BaoLin; Hong, Jun

2014-01-01

Direct electrochemistry of glucose oxidase (GOD) was achieved when an ionic liquid/GOD-Polyhydroxy-C60 functional membrane was confined on a glassy carbon electrode (GCE). The cyclic voltammograms (CVs) of the modified GCE showed a pair of redox peaks with a formal potential (E°') of - 329 ± 2 mV. The heterogeneous electron transfer constant (k(s)) was 1.43 s-1. The modified GCE response to glucose was linear in the range from 0.02 to 2.0 mM. The detection limit was 1 μM. The apparent Michaelis-Menten constant (K(m)(app)) was 1.45 mM.

Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells

DOEpatents

Ovshinsky, Stanford R.; Corrigan, Dennis; Venkatesan, Srini; Young, Rosa; Fierro, Christian; Fetcenko, Michael A.

1994-01-01

A high capacity, long cycle life positive electrode for use in an alkaline rechargeable electrochemical cell comprising: a solid solution nickel hydroxide material having a multiphase structure that comprises at least one polycrystalline .gamma.-phase including a polycrystalline .gamma.-phase unit cell comprising spacedly disposed plates with at least one chemical modifier incorporated around the plates, the plates having a range of stable intersheet distances corresponding to a 2.sup.+ oxidation state and a 3.5.sup.+, or greater, oxidation state; and at least one compositional modifier incorporated into the solid solution nickel hydroxide material to promote the multiphase structure.

Degradation of paracetamol by advance oxidation processes using modified reticulated vitreous carbon electrodes with TiO(2) and CuO/TiO(2)/Al(2)O(3).

PubMed

Arredondo Valdez, H C; García Jiménez, G; Gutiérrez Granados, S; Ponce de León, C

2012-11-01

The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO(2) and CuO/TiO(2)/Al(2)O(3) by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO(2)/RVC, 90% degradation was achieved in 2 h while with CuO/TiO(2)/Al(2)O(3)/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO(2)/RVC/UV and 99% with CuO/TiO(2)/Al(2)O(3)/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics. Copyright © 2012 Elsevier Ltd. All rights reserved.

Electrocatalytic oxidation of dopamine based on non-covalent functionalization of manganese tetraphenylporphyrin/reduced graphene oxide nanocomposite.

PubMed

Sakthinathan, Subramanian; Lee, Hsin Fang; Chen, Shen-Ming; Tamizhdurai, P

2016-04-15

In the present work, a reduced graphene oxide (RGO) supported manganese tetraphenylporphyrin (Mn-TPP) nanocomposite was electrochemically synthesized and used for the highly selective and sensitive detection of dopamine (DA). The nuclear magnetic resonance, scanning electron microscopy and elemental analysis were confirmed the successful formation of RGO/Mn-TPP nanocomposite. The prepared RGO/Mn-TPP nanocomposite modified electrode exhibited an enhanced electrochemical response to DA with less oxidation potential and enhanced response current. The electrochemical studies revealed that the oxidation of the DA at the composite electrode is a surface controlled process. The cyclic voltammetry, differential pulse voltammetry and amperometry methods were enable to detect DA. The working linear range of the electrode was observed from 0.3 to 188.8 μM, limit of detection was 8 nM and the sensitivity was 2.606 μA μM(-1) cm(-2). Here, the positively charged DA and negatively charged porphyrin modified RGO can accelerate the electrocatalysis of DA via electrostatic attraction, while the negatively charged ascorbic acid (AA) repulsed by the negatively charged electrode surface which supported for good selectivity. The good recovery results obtained for the determination of DA present in DA injection samples and human pathological sample further revealed the good practicality of RGO/Mn-TPP nanocomposite film modified electrode. Copyright © 2016 Elsevier Inc. All rights reserved.

Biofuel cells based on direct enzyme-electrode contacts using PQQ-dependent glucose dehydrogenase/bilirubin oxidase and modified carbon nanotube materials.

PubMed

Scherbahn, V; Putze, M T; Dietzel, B; Heinlein, T; Schneider, J J; Lisdat, F

2014-11-15

Two types of carbon nanotube electrodes (1) buckypaper (BP) and (2) vertically aligned carbon nanotubes (vaCNT) have been used for elaboration of glucose/O2 enzymatic fuel cells exploiting direct electron transfer. For the anode pyrroloquinoline quinone dependent glucose dehydrogenase ((PQQ)GDH) has been immobilized on [poly(3-aminobenzoic acid-co-2-methoxyaniline-5-sulfonic acid), PABMSA]-modified electrodes. For the cathode bilirubin oxidase (BOD) has been immobilized on PQQ-modified electrodes. PABMSA and PQQ act as promoter for enzyme bioelectrocatalysis. The voltammetric characterization of each electrode shows current densities in the range of 0.7-1.3 mA/cm(2). The BP-based fuel cell exhibits maximal power density of about 107 µW/cm(2) (at 490 mV). The vaCNT-based fuel cell achieves a maximal power density of 122 µW/cm(2) (at 540 mV). Even after three days and several runs of load a power density over 110 µW/cm(2) is retained with the second system (10mM glucose). Due to a better power exhibition and an enhanced stability of the vaCNT-based fuel cells they have been studied in human serum samples and a maximal power density of 41 µW/cm(2) (390 mV) can be achieved. Copyright © 2014 Elsevier B.V. All rights reserved.

Impedance spectroscopy study of a catechol-modified activated carbon electrode as active material in electrochemical capacitor

NASA Astrophysics Data System (ADS)

Cougnon, C.; Lebègue, E.; Pognon, G.

2015-01-01

Modified activated carbon (Norit S-50) electrodes with electrochemical double layer (EDL) capacitance and redox capacitance contributions to the electric charge storage were tested in 1 M H2SO4 to quantify the benefit and the limitation of the surface redox reactions on the electrochemical performances of the resulting pseudo-capacitive materials. The electrochemical performances of an electrochemically anodized carbon electrode and a catechol-modified carbon electrode, which make use both EDL capacitance of the porous structure of the carbon and redox capacitance, were compared to the performances obtained for the pristine carbon. Nitrogen gas adsorption measurements have been used for studying the impact of the grafting on the BET surface area, pore size distribution, pore volume and average pore diameter. The electrochemical behavior of carbon materials was studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The EIS data were discussed by using a complex capacitance model that allows defining the characteristic time constant, the global capacitance and the frequency at which the maximum charge stored is reached. The EIS measurements were achieved at different dc potential values where a redox activity occurs and the evolution of the capacitance and the capacitive relaxation time with the electrode potential are presented. Realistic galvanostatic charge/discharge measurements performed at different current rates corroborate the results obtained by impedance.

Performance-Enhanced Activated Carbon Electrodes for Supercapacitors Combining Both Graphene-Modified Current Collectors and Graphene Conductive Additive.

PubMed

Wang, Rubing; Qian, Yuting; Li, Weiwei; Zhu, Shoupu; Liu, Fengkui; Guo, Yufen; Chen, Mingliang; Li, Qi; Liu, Liwei

2018-05-15

Graphene has been widely used in the active material, conductive agent, binder or current collector for supercapacitors, due to its large specific surface area, high conductivity, and electron mobility. However, works simultaneously employing graphene as conductive agent and current collector were rarely reported. Here, we report improved activated carbon (AC) electrodes (AC@G@NiF/G) simultaneously combining chemical vapor deposition (CVD) graphene-modified nickel foams (NiF/Gs) current collectors and high quality few-layer graphene conductive additive instead of carbon black (CB). The synergistic effect of NiF/Gs and graphene additive makes the performances of AC@G@NiF/G electrodes superior to those of electrodes with CB or with nickel foam current collectors. The performances of AC@G@NiF/G electrodes show that for the few-layer graphene addition exists an optimum value around 5 wt %, rather than a larger addition of graphene, works out better. A symmetric supercapacitor assembled by AC@G@NiF/G electrodes exhibits excellent cycling stability. We attribute improved performances to graphene-enhanced conductivity of electrode materials and NiF/Gs with 3D graphene conductive network and lower oxidation, largely improving the electrical contact between active materials and current collectors.

Electrochemical characterisation and anodic stripping voltammetry at mesoporous platinum rotating disc electrodes.

PubMed

Lozano-Sanchez, Pablo; Elliott, Joanne M

2008-02-01

Using the technique of liquid crystal templating a rotating disc electrode (RDE) was modified with a high surface area mesoporous platinum film. The surface area of the electrode was characterised by acid voltammetry, and found to be very high (ca. 86 cm(2)). Acid characterisation of the electrode produced distorted voltammograms was interpreted as being due to the extremely large surface area which produced a combination of effects such as localised pH change within the pore environment and also ohmic drop effects. Acid voltammetry in the presence of two different types of surfactant, namely Tween 20 and Triton X-100, suggested antifouling properties associated with the mesoporous deposit. Further analysis of the modified electrode using a redox couple in solution showed typical RDE behaviour although extra capacitive currents were observed due to the large surface area of the electrode. The phenomenon of underpotential deposition was exploited for the purpose of anodic stripping voltammetry and results were compared with data collected for microelectrodes. Underpotential deposition of metal ions at the mesoporous RDE was found to be similar to that at conventional platinum electrodes and mesoporous microelectrodes although the rate of surface coverage was found to be slower at a mesoporous RDE. It was found that a mesoporous RDE forms a suitable system for quantification of silver ions in solution.

Performance-Enhanced Activated Carbon Electrodes for Supercapacitors Combining Both Graphene-Modified Current Collectors and Graphene Conductive Additive

PubMed Central

Wang, Rubing; Qian, Yuting; Li, Weiwei; Zhu, Shoupu; Liu, Fengkui; Guo, Yufen; Chen, Mingliang; Li, Qi; Liu, Liwei

2018-01-01

Graphene has been widely used in the active material, conductive agent, binder or current collector for supercapacitors, due to its large specific surface area, high conductivity, and electron mobility. However, works simultaneously employing graphene as conductive agent and current collector were rarely reported. Here, we report improved activated carbon (AC) electrodes (AC@G@NiF/G) simultaneously combining chemical vapor deposition (CVD) graphene-modified nickel foams (NiF/Gs) current collectors and high quality few-layer graphene conductive additive instead of carbon black (CB). The synergistic effect of NiF/Gs and graphene additive makes the performances of AC@G@NiF/G electrodes superior to those of electrodes with CB or with nickel foam current collectors. The performances of AC@G@NiF/G electrodes show that for the few-layer graphene addition exists an optimum value around 5 wt %, rather than a larger addition of graphene, works out better. A symmetric supercapacitor assembled by AC@G@NiF/G electrodes exhibits excellent cycling stability. We attribute improved performances to graphene-enhanced conductivity of electrode materials and NiF/Gs with 3D graphene conductive network and lower oxidation, largely improving the electrical contact between active materials and current collectors. PMID:29762528

Smart protein biogate as a mediator to regulate competitive host-guest interaction for sensitive ratiometric electrochemical assay of prion

NASA Astrophysics Data System (ADS)

Yu, Peng; Zhang, Xiaohua; Zhou, Jiawan; Xiong, Erhu; Li, Xiaoyu; Chen, Jinhua

2015-11-01

A novel competitive host-guest strategy regulated by protein biogate was developed for sensitive and selective analysis of prion protein. The methylene blue (MB)-tagged prion aptamer (MB-Apt) was introduced to the multiwalled carbon nanotubes-β-cyclodextrins (MWCNTs-β-CD) composites-modified glassy carbon (GC) electrode through the host-guest interaction between β-CD and MB. In the absence of prion, MB-Apt could be displaced by ferrocenecarboxylic acid (FCA) due to its stronger binding affinity to β-CD, resulting in a large oxidation peak of FCA. However, in the presence of prion, the specific prion-aptamer interaction drove the formation of protein biogate to seal the cavity of β-CD, which hindered the guest displacement of MB by FCA and resulted in the oxidation peak current of MB (IMB) increased and that of FCA (IFCA) decreased. The developed aptasensor showed good response towards the target (prion protein) with a low detection limit of 160 fM. By changing the specific aptamers, this strategy could be easily extended to detect other proteins, showing promising potential for extensive applications in bioanalysis.

Study of the interaction of 6-mercaptopurine with protein by microdialysis coupled with LC and electrochemical detection based on functionalized multi-wall carbon nanotubes modified electrode.

PubMed

Cao, Xu-Ni; Lin, Li; Zhou, Yu-Yan; Zhang, Wen; Shi, Guo-Yue; Yamamoto, Katsunobu; Jin, Li-Tong

2003-07-14

Microdialysis sampling coupled with liquid chromatography and electrochemical detection (LC-ECD) was developed and applied to study the interaction of 6-Mercaptopurine (6-MP) with bovine serum albumin (BSA). In the LC-ECD, the multi-wall carbon nanotubes fuctionalized with carboxylic groups modified electrode (MWNT-COOH CME) was used as the working electrode for the determination of 6-MP. The results indicated that this chemically modified electrode (CME) exhibited efficiently electrocatalytic oxidation for 6-MP with relatively high sensitivity, stability and long-life. The peak currents of 6-MP were linear to its concentrations ranging from 4.0 x 10(-7) to 1.0 x 10(-4) mol l(-1) with the calculated detection limit (S/N = 3) of 2.0 x 10(-7) mol l(-1). The method had been successfully applied to assess the association constant (K) and the number of the binding sites (n) on a BSA molecular, which calculated by Scatchard equation, were 3.97 x 10(3) mol(-1) l and 1.51, respectively. This method provided a fast, sensible and simple technique for the study of drug-protein interactions.

Preparation of Cu₂O-Reduced Graphene Nanocomposite Modified Electrodes towards Ultrasensitive Dopamine Detection.

PubMed

He, Quanguo; Liu, Jun; Liu, Xiaopeng; Li, Guangli; Deng, Peihong; Liang, Jing

2018-01-12

Cu₂O-reduced graphene oxide nanocomposite (Cu₂O-RGO) was used to modify glassy carbon electrodes (GCE), and applied for the determination of dopamine (DA). The microstructure of Cu₂O-RGO nanocomposite material was characterized by scanning electron microscope. Then the electrochemical reduction condition for preparing Cu₂O-RGO/GCE and experimental conditions for determining DA were further optimized. The electrochemical behaviors of DA on the bare electrode, RGO- and Cu₂O-RGO-modified electrodes were also investigated using cyclic voltammetry in phosphate-buffered saline solution (PBS, pH 3.5). The results show that the oxidation peaks of ascorbic acid (AA), dopamine (DA), and uric acid (UA) could be well separated and the peak-to-peak separations are 204 mV (AA-DA) and 144 mV (DA-UA), respectively. Moreover, the linear response ranges for the determination of 1 × 10 -8 mol/L~1 × 10 -6 mol/L and 1 × 10 -6 mol/L~8 × 10 -5 mol/L with the detection limit 6.0 × 10 -9 mol/L (S/N = 3). The proposed Cu₂O-RGO/GCE was further applied to the determination of DA in dopamine hydrochloride injections with satisfactory results.

An electrocatalytic oxidation and voltammetric method using a chemically reduced graphene oxide film for the determination of caffeic acid.

PubMed

Vilian, A T Ezhil; Chen, Shen-Ming; Chen, Ying-Hui; Ali, M Ajmal; Al-Hemaid, Fahad M A

2014-06-01

The present work describes the characterization of a chemically reduced graphene oxide (CRGO) modified glassy carbon electrode (GCE) for electrochemical investigation of caffeic acid (CA). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), amperometry, and electrochemical impedance spectroscopy (EIS) techniques were used to characterize the properties of the electrode. There was an obvious enhancement of the current response and a decreased over potential for the oxidation of CA. The interfacial electron transfer rate of CA was studied by EIS. Under optimal conditions, the CRGO displayed a linear response range of 1×10(-8) to 8×10(-4) M and the detection limit was 2×10(-9) M (S/N=3), with a sensitivity of 192.21 μA mM(-1) cm(-2) at an applied potential of +0.2V (vs. Ag/AgCl reference), which suggests that the CRGO is a promising sensing materials for the electrochemical investigation of CA. The results showed the good sensitivity, selectivity and high reproducibility of the CRGO modified electrode. Moreover, this modified electrode was further applied to investigate the CA in real samples of wine with satisfactory results. Copyright © 2014 Elsevier Inc. All rights reserved.

Improved photocurrent of a poly (3,4-ethylenedioxythiophene)-ClO₄⁻/TiO₂ thin film-modified counter electrode for dye-sensitized solar cells.

PubMed

Sakurai, Sho; Kawamata, Yuka; Takahashi, Masashi; Kobayashi, Koichi

2011-01-01

We prepared a poly(3,4-ethylenedioxythiophene) (PEDOT)-ClO₄⁻-supported TiO₂ thin-film electrode as a counter electrode on a transparent conductive oxide glass electrode for a dye-sensitized solar cell (DSSC) using a combination of sol-gel and electropolymerization methods. The photocurrent-voltage characteristics indicate that DSSCs with PEDOT-ClO₄⁻/TiO₂ thin-film counter electrodes had a high photovoltaic conversion efficiency similar to that of PEDOT-ClO₄⁻/TiO₂ particle composite-film electrodes. Furthermore, it was found that the photocurrent was increased by attaching a reflector to the opposite side of the transparent counter electrode.

Efficient recyclable organic solar cells on cellulose nanocrystal substrates with a conducting polymer top electrode deposited by film-transfer lamination

Treesearch

Yinhua Zhou; Talha M. Khan; Jen-Chieh Liu; Canek Fuentes-Hernandez; Jae Won Shim; Ehsan Najafabadi; Jeffrey P. Youngblood; Robert J. Moon; Bernard Kippelen

2014-01-01

We report on efficient solar cells on recyclable cellulose nanocrystal (CNC) substrates with a new device structure wherein polyethylenimine-modified Ag is used as the bottom electron-collecting electrode and high-conductivity poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS, PH1000) is used as the semitransparent top holecollecting electrode. The...

Characteristics of a corona discharge with a hot corona electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulumbaev, E. B.; Lelevkin, V. M.; Niyazaliev, I. A.

The effect of the temperature of the corona electrode on the electrical characteristics of a corona discharge was studied experimentally. A modified Townsend formula for the current-voltage characteristic of a one-dimensional corona is proposed. Gasdynamic and thermal characteristics of a positive corona discharge in a coaxial electrode system are calculated. The calculated results are compared with the experimental data.

RuO2/Activated Carbon Composite Electrode Prepared by Modified Colloidal Procedure and Thermal Decomposition Method

NASA Astrophysics Data System (ADS)

Li, Xiang; Zheng, Feng; Gan, Weiping; Luo, Xun

2016-01-01

RuO2/activated carbon (AC) composite electrode was prepared by a modified colloidal procedure and a thermal decomposition method. The precursor for RuO2/AC was coated on tantalum sheet and annealed at 150°C to 190°C for 3 h to develop thin-film electrode. The microstructure and morphology of the RuO2/AC film were characterized by thermogravimetric analysis (TGA), x-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM). The TGA results showed the maximum loss of RuO2/AC composite film at 410°C, with residual RuO2 of 23.17 wt.%. The amorphous phase structure of the composite was verified by XRD analysis. SEM analysis revealed that fine RuO2 particles were dispersed in an activated carbon matrix after annealing. The electrochemical properties of RuO2/AC electrode were examined by cycling voltammetry, galvanostatic charge-discharge, and cyclic behavior measurements. The specific capacitance of RuO2/AC electrode reached 245 F g-1. The cyclic behavior of RuO2/AC electrode was stable. Optimal annealing was achieved at 170°C for 3 h.

Fabrication and Characterization of a Stabilized Thin Film Ag/AgCl Reference Electrode Modified with Self-Assembled Monolayer of Alkane Thiol Chains for Rapid Biosensing Applications.

PubMed

Rahman, Tanzilur; Ichiki, Takanori

2017-10-13

The fabrication of miniaturized electrical biosensing devices can enable the rapid on-chip detection of biomarkers such as miRNA molecules, which is highly important in early-stage cancer detection. The challenge in realizing such devices remains in the miniaturization of the reference electrodes, which is an integral part of electrical detection. Here, we report on a novel thin film Ag/AgCl reference electrode (RE) that has been fabricated on top of a Au-sputtered glass surface, which was coated with a self-assembled monolayer (SAM) of 6-mercepto-1-hexanol (MCH). The electrode showed very little measurement deviation (-1.5 mv) from a commercial Ag/AgCl reference electrode and exhibited a potential drift of only ± 0.2 mV/h. In addition, the integration of this SAM-modified microfabricated thin film RE enabled the rapid detection (<30 min) of miRNA (let-7a). The electrode can be integrated seamlessly into a microfluidic device, allowing the highly stable and fast measurement of surface potential and is expected to be very useful for the development of miniature electrical biosensors.

Photocatalysis and self-cleaning from g-C3N4 coated cotton fabrics under sunlight irradiation

NASA Astrophysics Data System (ADS)

Fan, Yunde; Zhou, Ji; Zhang, Jin; Lou, Yaqin; Huang, Zhenwu; Ye, Yong; Jia, Li; Tang, Bin

2018-05-01

Graphite-like carbon nitride (g-C3N4) nanosheets have been facilely assembled via electrostatic interaction onto cotton fabrics for achieving multi-functionalities. The surface morphologies, chemical composition and optical features of the g-C3N4-coated fabrics were characterized. The treated cotton fabrics exhibited remarkable photocatalytic degradation activity and superior self-cleaning performance. A complete degradation of Rhodamine B (RhB) and removal of stains were accomplished under simulated sunlight irradiation. More importantly, the modified fabrics can be reused in catalysis reactions with great durability. The practical treatment approach demonstrated from this work has great potential to be applied in textile industry for functional fabrics manufacture.

Electrochemical properties of the erbium-chitosan-fluorine-modified PbO2 electrode for the degradation of 2,4-dichlorophenol in aqueous solution.

PubMed

Wang, Ying; Shen, Zhenyao; Li, Yang; Niu, Junfeng

2010-05-01

The erbium (Er)-chitosan-fluorine (F) modified PbO(2) electrode was prepared by electrodeposition method, and its use for adsorption and electrochemical degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous solution was compared with F-PbO(2) and Er-F-PbO(2) electrodes in a batch experiment. The electrodes were characterized by scanning electron microscopy, X-ray diffraction and cyclic voltammetry. Degradation of 2,4-DCP depending on Er and chitosan contents was discussed. The results showed that Er(2)O(3) and chitosan were scattered between the prevailing crystal structure of beta-PbO(2) and thus decreased the internal stress of PbO(2) film. Prior to each electrolysis, the modified PbO(2) anode was first pre-saturated with 2,4-DCP solution for 360 min to preclude the 2,4-DCP decrease due to adsorption. Among the electrodes examined in our study, the highest adsorption and electrochemical degradation for 2,4-DCP and TOC removals that are due to oxidation and adsorption of the organic products onto the chitosan was observed on Er-chitosan-F-PbO(2) electrode. At an applied current density of 5 mAcm(-2), the removal percentages of 2,4-DCP and TOC (solution volume: 180 mL, initial 2,4-DCP concentration: 90 mgL(-1)) were 95% after 120 min and 53% after 360 min, respectively. At Er amount of 10mM in the precursor coating solution, the degradation and mineralization removal for 2,4-DCP on the Er-F-PbO(2) electrode reached a maximum. At chitosan amount of 5 gL(-1), the highest TOC removal on the Er-chitosan-F-PbO(2) electrode was observed. Intermediates mainly including aliphatic carboxylic acids were examined and a possible degradation pathway for 2,4-DCP in aqueous solution involving dechlorination and hydroxylation reactions was proposed. Copyright 2010 Elsevier Ltd. All rights reserved.

Nickel hydroxide nanoparticles-reduced graphene oxide nanosheets film: layer-by-layer electrochemical preparation, characterization and rifampicin sensory application.

PubMed

Rastgar, Shokoufeh; Shahrokhian, Saeed

2014-02-01

Electrochemical deposition, as a well-controlled synthesis procedure, has been used for subsequently layer-by-layer preparation of nickel hydroxide nanoparticle-reduced graphene oxide nanosheets (Ni(OH)2-RGO) on a graphene oxide (GO) film pre-cast on a glassy carbon electrode surface. The surface morphology and nature of the nano-hybrid film (Ni(OH)2-RGO) was thoroughly characterized by scanning electron and atomic force microscopy, spectroscopy and electrochemical techniques. The modified electrode appeared as an effective electro-catalytic model for analysis of rifampicin (RIF) by using linear sweep voltammetry (LSV). The prepared modified electrode exhibited a distinctly higher activity for electro-oxidation of RIF than either GO, RGO nanosheets or Ni(OH)2 nanoparticles. Enhancement of peak currents is ascribed to the fast heterogeneous electron transfer kinetics that arise from the synergistic coupling between the excellent properties of RGO nanosheets (such as high density of edge plane sites, subtle electronic characteristics and attractive π-π interaction) and unique properties of metal nanoparticles. Under the optimized analysis conditions, the modified electrode showed two oxidation processes for rifampicin at potentials about 0.08 V (peak I) and 0.69 V (peak II) in buffer solution of pH 7.0 with a wide linear dynamic range of 0.006-10.0 µmol L(-1) and 0.04-10 µmol L(-1) with a detection limit of 4.16 nmol L(-1) and 2.34 nmol L(-1) considering peaks I and II as an analytical signal, respectively. The results proved the efficacy of the fabricated modified electrode for simple, low cost and highly sensitive medicine sensor well suited for the accurate determinations of trace amounts of rifampicin in the pharmaceutical and clinical preparations. © 2013 Elsevier B.V. All rights reserved.

Nonenzymatic electrochemical detection of glucose using well-distributed nickel nanoparticles on straight multi-walled carbon nanotubes.

PubMed

Nie, Huagui; Yao, Zhen; Zhou, Xuemei; Yang, Zhi; Huang, Shaoming

2011-12-15

A nonenzymatic electrochemical sensor device was fabricated for glucose detection based on nickel nanoparticles (NiNPs)/straight multi-walled carbon nanotubes (SMWNTs) nanohybrids, which were synthesized through in situ precipitation procedure. SMWNTs can be easily dispersed in solution after mild sonication pretreatment, which facilitates the precursor of NiNPs binding to their surface and results in the homogeneous distribution of NiNPs on the surface of SMWNTs. The morphology and component of the nanohybrids were characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD), respectively. Cyclic voltammetry (CV) and amperometry were used to evaluate the catalytic activity of the NiNPs/SMWNTs nanohybrids modified electrode towards glucose. It was found that the nanohybrids modified electrode showed remarkably enhanced electrocatalytic activity towards the oxidation of glucose in alkaline solution compared to that of the bare glass carbon electrode (GCE), the NiNPs and the SMWNTs modified electrode, attributing to the synergistic effect of SMWNTs and Ni(2+)/Ni(3+) redox couple. Under the optimal detection conditions, the as-prepared sensors exhibited linear behavior in the concentration range from 1 μM to 1 mM for the quantification of glucose with a limit of detection of 500 nM (3σ). Moreover, the NiNPs/SMWNTs modified electrode was also relatively insensitive to commonly interfering species such as ascorbic acid (AA), uric acid (UA), dopamine (DA), galactose (GA), and xylose (XY). The robust selectivities, sensitivities, and stabilities determined experimentally indicated the great potential of NiNPs/SMWNTs nanohybrids for construction of a variety of electrochemical sensors. Copyright © 2011 Elsevier B.V. All rights reserved.

Photo-electrochemical communication between cyanobacteria (Leptolyngbia sp.) and osmium redox polymer modified electrodes.

PubMed

Hasan, Kamrul; Bekir Yildiz, Huseyin; Sperling, Eva; Conghaile, Peter Ó; Packer, Michael A; Leech, Dónal; Hägerhäll, Cecilia; Gorton, Lo

2014-12-07

Photosynthetic microbial fuel cells (PMFCs) are an emerging technology for renewable solar energy conversion. Major efforts have been made to explore the electrogenic activity of cyanobacteria, mostly using practically unsustainable reagents. Here we report on photocurrent generation (≈8.64 μA cm(-2)) from cyanobacteria immobilized on electrodes modified with an efficient electron mediator, an Os(2+/3+) redox polymer. Upon addition of ferricyanide to the electrolyte, cyanobacteria generate the maximum current density of ≈48.2 μA cm(-2).

Deliberate modification of the solid electrolyte interphase (SEI) during lithiation of magnetite, Fe 3O 4: impact on electrochemistry

DOE PAGES

Bock, David C.; Marschilok, Amy C.; Takeuchi, Kenneth J.; ...

2017-11-20

Here, magnetite is a conversion anode material displaying multi-electron transfer during lithiation and delithiation. The solid electrolyte interphase (SEI) on magnetite, Fe 3O 4, electrodes for lithium ion batteries was deliberately modified through the use of fluoroethylene carbonate (FEC) electrolyte additive, improving both capacity retention and rate capability. Analysis showed reduction of FEC at higher voltage compared to non-fluorinated solvents with formation of a modified lithium flouride containing electrode surface.

A theoretical consideration of ion size effects on the electric double layer and voltammetry of nanometer-sized disk electrodes.

PubMed

Gao, Yu; Liu, Yuwen; Chen, Shengli

2016-12-12

Considering that an electric-double-layer (EDL) structure may significantly impact on the mass transport and charge transfer kinetics at the interfaces of nanometer-sized electrodes, while EDL structures could be altered by the finite sizes of electrolyte and redox ions, the possible effects of ion sizes on EDL structures and voltammetric responses of nanometer-sized disk (nanodisk) electrodes are investigated. Modified Boltzmann and Nernst-Planck (NP) equations, which include the influence of the finite ion volumes, are combined with the Poisson equation and modified Butler-Volmer equation to gain knowledge on how the finite sizes of ions and the nanometer sizes of electrodes may couple with each other to affect the structures and reactivities of a nanoscale electrochemical interface. Two typical ion radii, 0.38 nm and 0.68 nm, which could represent the sizes of the commonly used aqueous electrolyte ions (e.g., the solvated K + ) and the organic electrolyte ions (e.g., the solvated TEA + ) respectively, are considered. The finite size of ions can result in decreased screening of electrode charges, therefore magnifying EDL effects on the ion transport and the electron transfer at electrochemical interfaces. This finite size effect of ions becomes more pronounced for larger ions and at smaller electrodes as the electrode radii is larger than 10 nm. For electrodes with radii smaller than 10 nm, however, the ion size effect may be less pronounced with decreasing the electrode size. This can be explained in terms of the increased edge effect of disk electrodes at nanometer scales, which could relax the ion crowding at/near the outer Helmholtz plane. The conditions and situations under which the ion sizes may have a significant effect on the voltammetry of electrodes are discussed.

Highly selective direct determination of chlorate ions by using a newly developed potentiometric electrode based on modified smectite.

PubMed

Topcu, Cihan

2016-12-01

A novel polyvinyl chloride membrane chlorate (ClO 3 - ) selective electrode based on modified smectite was developed for the direct determination of chlorate ions and the potentiometric performance characteristics of its were examined. The best selectivity and sensitivity for chlorate ions were obtained for the electrode membrane containing ionophore/polyvinylchloride/o-nitrophenyloctylether in composition of 12/28/60 (w/w%). The proposed electrode showed a Nernstian response toward chlorate ions at pH=7 in the concentration range of 1×10 -7 -1×10 -1 M and the limit of detection was calculated as 9×10 -8 M from the constructed response plot. The linear slope of the electrode was -61±1mVdecade -1 for chlorate activity in the mentioned linear working range. The selectivity coefficients were calculated according to both the matched potential method and the separate solution method. The calculated selectivity coefficients showed that the electrode performed excellent selectivity for chlorate ions. The potentiometric response of electrode toward chlorate ions was found to be highly reproducible. The electrode potential was stable between pH=4-10 and it had a dynamic response time of <5s. The potentiometric behavior of the electrode in partial non-aqueous medium was also investigated and the obtained results (up to 5% (v/v) alcohol) were satisfactory. The proposed electrode was used during 15 weeks without any significant change in its potential response. Additionally, the electrode was very useful in water analysis studies such as dam water, river water, tap water, and swimming pool water where the direct determination of chlorate ions was required. Copyright © 2016 Elsevier B.V. All rights reserved.

Site selective generation of sol-gel deposits in layered bimetallic macroporous electrode architectures.

PubMed

Lalo, Hélène; Bon-Saint-Côme, Yémima; Plano, Bernard; Etienne, Mathieu; Walcarius, Alain; Kuhn, Alexander

2012-02-07

The elaboration of an original composite bimetallic macroporous electrode containing a site-selective sol-gel deposit is reported. Regular colloidal crystals, obtained by a modified Langmuir-Blodgett approach, are used as templates for the electrogeneration of the desired metals in the form of a well-defined layered bimetallic porous electrode. This porous matrix shows a spatially modulated electroactivity which is subsequently used as a strategy for targeted electrogeneration of a sol-gel deposit, exclusively in one predefined part of the porous electrode.

Retinal cell imaging in myopic chickens using adaptive optics multiphoton microscopy.

PubMed

Bueno, Juan M; Palacios, Raquel; Giakoumaki, Anastasia; Gualda, Emilio J; Schaeffel, Frank; Artal, Pablo

2014-03-01

Abnormal eye growth induced by visual deprivation can modify the structure and density of the retinal cells. We have used an adaptive optics multiphoton microscope to image photoreceptors (PRs) and ganglion cells (GCs) at different retinal locations in unstained retinas of chicken eyes with about 10D of myopia and their normal-sighted fellow eyes. In all samples, the local averaged inter-PR distance increased with eccentricity. No significant differences in PR density were found between control and myopic eyes. GC density declined in myopic eyes compared to control eyes and the inter-cell distance increased. In normal eyes, the size of the GC cell bodies increased approximately two-fold between the area centralis and the peripheral retina. In myopic eyes, this trend was preserved but the GC bodies were larger at each retinal location, compared to control eyes. Obviously, GC morphology is changing when the retinal area is enlarged in myopic eyes.

Retinal cell imaging in myopic chickens using adaptive optics multiphoton microscopy

PubMed Central

Bueno, Juan M.; Palacios, Raquel; Giakoumaki, Anastasia; Gualda, Emilio J.; Schaeffel, Frank; Artal, Pablo

2014-01-01

Abnormal eye growth induced by visual deprivation can modify the structure and density of the retinal cells. We have used an adaptive optics multiphoton microscope to image photoreceptors (PRs) and ganglion cells (GCs) at different retinal locations in unstained retinas of chicken eyes with about 10D of myopia and their normal-sighted fellow eyes. In all samples, the local averaged inter-PR distance increased with eccentricity. No significant differences in PR density were found between control and myopic eyes. GC density declined in myopic eyes compared to control eyes and the inter-cell distance increased. In normal eyes, the size of the GC cell bodies increased approximately two-fold between the area centralis and the peripheral retina. In myopic eyes, this trend was preserved but the GC bodies were larger at each retinal location, compared to control eyes. Obviously, GC morphology is changing when the retinal area is enlarged in myopic eyes. PMID:24688804

BDNF-TrkB signaling through Erk1/2MAPK phosphorylation mediates the enhancement of fear memory induced by glucocorticoids

PubMed Central

Revest, J-M; Le Roux, A; Roullot-Lacarrière, V; Kaouane, N; Vallée, M; Kasanetz, F; Rougé-Pont, F; Tronche, F; Desmedt, A; Piazza, P V

2014-01-01

Activation of glucocorticoid receptors (GR) by glucocorticoid hormones (GC) enhances contextual fear memories through the activation of the Erk1/2MAPK signaling pathway. However, the molecular mechanism mediating this effect of GC remains unknown. Here we used complementary molecular and behavioral approaches in mice and rats and in genetically modified mice in which the GR was conditionally deleted (GRNesCre). We identified the tPA-BDNF-TrkB signaling pathway as the upstream molecular effectors of GR-mediated phosphorylation of Erk1/2MAPK responsible for the enhancement of contextual fear memory. These findings complete our knowledge of the molecular cascade through which GC enhance contextual fear memory and highlight the role of tPA-BDNF-TrkB-Erk1/2MAPK signaling pathways as one of the core effectors of stress-related effects of GC. PMID:24126929

Electrochemical and in vitro neuronal recording characteristics of multi-electrode arrays surface-modified with electro-co-deposited gold-platinum nanoparticles.

PubMed

Kim, Yong Hee; Kim, Ah Young; Kim, Gook Hwa; Han, Young Hwan; Chung, Myung-Ae; Jung, Sang-Don

2016-02-01

In order to complement the high impedance electrical property of gold nanoparticles (Au NPs) we have performed electro-co-deposition of gold-platinum nanoparticles (Au-Pt NPs) onto the Au multi-electrode array (MEA) and modified the Au-Pt NPs surface with cell adhesive poly-D-lysine via thiol chemistry based covalent binding. The Au-Pt NPs were analyzed to have bimetallic nature not the mixture of Au NPs and Pt NPs by X-ray diffraction analysis and to have impedance value (4.0 × 10(4) Ω (at 1 kHz)) comparable to that of Pt NPs. The performance of Au-Pt NP-modified MEAs was also checked in relation to neuronal signal recording. The noise level in Au-Pt NP-modified MEAs was lower than in that of Au NP-modified MEA.

Chemically modified electrodes by nucleophilic substitution of chlorosilylated platinum oxide surfaces

NASA Astrophysics Data System (ADS)

Chen, Chun-Hsien; Hutchison, James H.; Postlethwaite, Timothy A.; Richardson, John N.; Murray, R. W.

1994-07-01

Chlorosilylated platinum oxide electrode surfaces can be generated by reaction of SiCl4 vapor with an electrochemically prepared monolayer of platinum oxide. A variety of nucleophilic agents (such as alcohols, amines, thiols, and Grignard reagents) can be used to displace chloride and thereby functionalize the metal surface. Electroactive surfaces prepared with ferrocene methanol as the nucleophile show that derivatization by small molecules can achieve coverages on the order of a full monolayer. Surfaces modified with long-chain alkyl groups efficiently block electrode reactions of redox probes dissolved in the contacting solution, but other electrochemical (double layer capacitance and surface coverage) and contact angle measurements suggest that these molecule films are not highly ordered, self-assembled monolayers.

Carbon paste electrode with covalently immobilized thionine for electrochemical sensing of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Thenmozhi, K.; Sriman Narayanan, S.

2017-11-01

A water-soluble redox mediator, thionin was covalently immobilized to the functionalized graphite powder and a carbon paste electrode was fabricated from this modified graphite powder. The immobilization procedure proved to be effective in anchoring the thionin mediator in the graphite electrode setup without any leakage problem during the electrochemical studies. The covalent immobilization of the thionin mediator was studied with FT-IR and the electrochemical response of the thionin carbon paste electrode was optimized on varying the supporting electrolyte, pH and scan rate. The modified electrode exhibited well-defined electrocatalytic activity towards the reduction of H2O2 at a lower potential of -0.266 V with good sensitivity. The developed amperometric sensor was efficient towards H2O2 in the linear range from 2.46 × 10-5 M to 4.76 × 10-3 M, with a detection limit of 1.47 × 10-5 M respectively. Important advantages of this sensor are its excellent electrochemical performance, simple fabrication, easy renewability, reproducible analytical results, acceptable accuracy and good operational and long-term stability.

Construction of an electrode modified with gallium(III) for voltammetric detection of ovalbumin.

PubMed

Sugawara, Kazuharu; Okusawa, Makoto; Takano, Yusaku; Kadoya, Toshihiko

2014-01-01

Electrodes modified with gallium(III) complexes were constructed to detect ovalbumin (OVA). For immobilization of a gallium(III)-nitrilotriacetate (NTA) complex, the electrode was first covered with collagen film. After the amino groups of the film had reacted with isothiocyanobenzyl-NTA, the gallium(III) was then able to combine with the NTA moieties. Another design featured an electrode cast with a gallium(III)-acetylacetonate (AA) complex. The amount of gallium(III) in the NTA complex was equivalent to one-quarter of the gallium(III) that could be utilized from an AA complex. However, the calibration curves of OVA using gallium(III)-NTA and gallium(III)-AA complexes were linear in the ranges of 7.0 × 10(-11) - 3.0 × 10(-9) M and 5.0 × 10(-10) - 8.0 × 10(-9) M, respectively. The gallium(III) on the electrode with NTA complex had high flexibility due to the existence of a spacer between the NTA and the collagen film, and, therefore, the reactivity of the gallium(III) to OVA was superior to that of the gallium(III)-AA complex with no spacer.

Spontaneous modification of carbon surface with neutral red from its diazonium salts for bioelectrochemical systems.

PubMed

Guo, Kun; Chen, Xin; Freguia, Stefano; Donose, Bogdan C

2013-09-15

This study introduces a novel and simple method to covalently graft neutral red (NR) onto carbon surfaces based on spontaneous reduction of in situ generated NR diazonium salts. Immobilization of neutral red on carbon surface was achieved by immersing carbon electrodes in NR-NaNO2-HCl solution. The functionalized electrodes were characterized by cyclic voltammetry (CV), atomic force microscope (AFM), and X-ray photoelectron spectroscopy (XPS). Results demonstrated that NR attached in this way retains high electrochemical activity and proved that NR was covalently bound to the carbon surface via the pathway of reduction of aryl diazonium salts. The NR-modified electrodes showed a good stability when stored in PBS solution in the dark. The current output of an acetate-oxidising microbial bioanode made of NR-modified graphite felts were 3.63±0.36 times higher than the unmodified electrodes, which indicates that covalently bound NR can act as electron transfer mediator to facilitate electron transfer from bacteria to electrodes. Copyright © 2013 Elsevier B.V. All rights reserved.

Constructing effective photocatalytic purification system with P-introduced g-C3N4 for elimination of UO22+

NASA Astrophysics Data System (ADS)

Wu, Xi; Jiang, Shujuan; Song, Shaoqing; Sun, Chuanzhi

2018-02-01

Due to the inherent defects of precursor molecular structure, the limited effect of structure in the formed g-C3N4 will weaken the extension of delocalization of π electrons between the adjacent tri-s-triazine or heptazine units of g-C3N4, which thus leads to poor visible-light absorption, low utilization efficiency of charge carrier. Herein, P-introduced g-C3N4 (PC3N4) photocatalysts were constructed by partially replacing C with tributyl phosphate as precursor, and the as-designed PC3N4 photocatalysts were used to eliminate aqueous uranyl ion by photocatalytic reduction technology under visible-light irradiation. Experimental and DFT revealed that introduction of P into g-C3N4 significantly modified its electronic structure, as reflected by the narrowed band gap, enhanced visible-light absorption as well as improved transfer capability of photogenerated charge. Therefore, photocatalytic activity of PC3N4 was much better than that of pristine g-C3N4 and conventional reducing-type photocatalysts. This study suggests an efficient strategy for construct effective visible-light-responsive photocatalysts for radioactive environmental remediation.

A single high dose of dexamethasone affects the phosphorylation state of glutamate AMPA receptors in the human limbic system

PubMed Central

Lopes, M W; Leal, R B; Guarnieri, R; Schwarzbold, M L; Hoeller, A; Diaz, A P; Boos, G L; Lin, K; Linhares, M N; Nunes, J C; Quevedo, J; Bortolotto, Z A; Markowitsch, H J; Lightman, S L; Walz, R

2016-01-01

Glucocorticoids (GC) released during stress response exert feedforward effects in the whole brain, but particularly in the limbic circuits that modulates cognition, emotion and behavior. GC are the most commonly prescribed anti-inflammatory and immunosuppressant medication worldwide and pharmacological GC treatment has been paralleled by the high incidence of acute and chronic neuropsychiatric side effects, which reinforces the brain sensitivity for GC. Synapses can be bi-directionally modifiable via potentiation (long-term potentiation, LTP) or depotentiation (long-term depression, LTD) of synaptic transmission efficacy, and the phosphorylation state of Ser831 and Ser845 sites, in the GluA1 subunit of the glutamate AMPA receptors, are a critical event for these synaptic neuroplasticity events. Through a quasi-randomized controlled study, we show that a single high dexamethasone dose significantly reduces in a dose-dependent manner the levels of GluA1-Ser831 phosphorylation in the amygdala resected during surgery for temporal lobe epilepsy. This is the first report demonstrating GC effects on key markers of synaptic neuroplasticity in the human limbic system. The results contribute to understanding how GC affects the human brain under physiologic and pharmacologic conditions. PMID:27959333

Coated carbon nanotube array electrodes

DOEpatents

Ren, Zhifeng; Wen, Jian; Chen, Jinghua; Huang, Zhongping; Wang, Dezhi

2006-12-12

The present invention provides conductive carbon nanotube (CNT) electrode materials comprising aligned CNT substrates coated with an electrically conducting polymer, and the fabrication of electrodes for use in high performance electrical energy storage devices. In particular, the present invention provides conductive CNTs electrode material whose electrical properties render them especially suitable for use in high efficiency rechargeable batteries. The present invention also provides methods for obtaining surface modified conductive CNT electrode materials comprising an array of individual linear, aligned CNTs having a uniform surface coating of an electrically conductive polymer such as polypyrrole, and their use in electrical energy storage devices.

Coated carbon nanotube array electrodes

DOEpatents

Ren, Zhifeng [Newton, MA; Wen, Jian [Newton, MA; Chen, Jinghua [Chestnut Hill, MA; Huang, Zhongping [Belmont, MA; Wang, Dezhi [Wellesley, MA

2008-10-28

The present invention provides conductive carbon nanotube (CNT) electrode materials comprising aligned CNT substrates coated with an electrically conducting polymer, and the fabrication of electrodes for use in high performance electrical energy storage devices. In particular, the present invention provides conductive CNTs electrode material whose electrical properties render them especially suitable for use in high efficiency rechargeable batteries. The present invention also provides methods for obtaining surface modified conductive CNT electrode materials comprising an array of individual linear, aligned CNTs having a uniform surface coating of an electrically conductive polymer such as polypyrrole, and their use in electrical energy storage devices.

MicroRNA-495-3p functions as a tumor suppressor by regulating multiple epigenetic modifiers in gastric carcinogenesis.

PubMed

Eun, Jung Woo; Kim, Hyung Seok; Shen, Qingyu; Yang, Hee Doo; Kim, Sang Yean; Yoon, Jung Hwan; Park, Won Sang; Lee, Jung Young; Nam, Suk Woo

2018-01-01

MicroRNAs (miRNAs) engage in complex interactions with the machinery that controls the transcriptome and concurrently target multiple mRNAs. Here, we demonstrate that microRNA-495-3p (miR-495-3p) functions as a potent tumor suppressor by governing ten oncogenic epigenetic modifiers (EMs) in gastric carcinogenesis. From the large cohort transcriptome datasets of gastric cancer (GC) patients available from The Cancer Genome Atlas (TCGA) and the National Center for Biotechnology Information (NCBI) Gene Expression Omnibus (GEO), we were able to recapitulate 15 EMs as significantly overexpressed in GC among the 51 EMs that were previously reported to be involved in cancer progression. Computational target prediction yielded miR-495-3p, which targets as many as ten of the 15 candidate oncogenic EMs. Ectopic expression of miRNA mimics in GC cells caused miR-495-3p to suppress ten EMs, and inhibited tumor cell growth and proliferation via caspase-dependent and caspase-independent cell death processing. In addition, in vitro metastasis assays showed that miR-495-3p plays a role in the metastatic behavior of GC cells by regulating SLUG, vimentin, and N-cadherin. Furthermore, treatment of GC cells with 5-aza-2'-deoxcytidine restored miR-495-3p expression; sequence analysis revealed hypermethylation of the miR-495-3p promoter region in GC cells. A negative regulatory loop is proposed, whereby DNMT1, among ten oncogenic EMs, regulates miR-495-3p expression via hypermethylation of the miR-495-3p promoter. Our findings suggest that the functional loss or suppression of miR-495-3p triggers overexpression of multiple oncogenic EMs, and thereby contributes to malignant transformation and growth of gastric epithelial cells. Copyright © 2017 Pathological Society of Great Britain and Ireland. Published by John Wiley & Sons, Ltd. Copyright © 2017 Pathological Society of Great Britain and Ireland. Published by John Wiley & Sons, Ltd.

Detection of mercury ions using L-cysteine modified electrodes by anodic stripping voltammetric method

NASA Astrophysics Data System (ADS)

Vanitha, M.; Balasubramanian, N.; Joni, I. Made; Panatarani, Camellia

2018-02-01

The detection of contaminants in wastewater is of massive importance in today's situation as they pose a serious threat to the environment as well as humans. One such vital contaminants is mercury and its compound, the reported mercury detectors grieve from low sensitivity, high cost and slow response. In the present work graphene based electrode material is developed for sensing mercury contaminants in wastewater using electrochemical technique. The synthesized material graphene oxide (GO) modified with L-Cysteine in presence of polyvinylpyrrolidone (PVP) as capping agent was characterized using SEM, TEM and Raman Spectroscopic analysis. It is ascertained from the morphological characterization that the nanocomposite exhibits a spherical morphology. The L-cysteine modified graphene oxide electrode is electrochemically characterized using redox couple [Fe(CN)63-/4-] and electrochemical impedance spectroscopic (EIS) analysis. Electrochemical sensing of Hg (II) ions in solution was done using Square wave anodic stripping voltammetry (SWASV). The incorporation of graphene significantly increases the sensitivity and selectivity towards mercury sensing.

Determination of fenitrothion in water using a voltammetric sensor based on a polymer-modified glassy carbon electrode.

PubMed

Amare, Meareg; Abicho, Samuel; Admassie, Shimelis

2014-01-01

A glassy carbon electrode (GCE) modified with poly(4-amino-3-hydroxynaphthalene sulfonic acid) (poly-AHNSA) was used for the selective and sensitive determination of fenitrothion (FT) organophosphorus pesticide in water. The electrochemical behavior of FT at the bare GCE and the poly-AHNSA/GCE were compared using cyclic voltammetry. Enhanced peak current response and shift to a lower potential at the polymer-modified electrode indicated the electrocatalytic activity of the polymer film towards FT. Under optimized solution and method parameters, the adsorptive stripping square wave voltammetric reductive peak current of FT was linear to FT concentration in the range of 0.001 to 6.6 x 10(-6) M, and the LOD obtained (3delta/m) was 7.95 x 10(-10) M. Recoveries in the range 96-98% of spiked FT in tap water and reproducible results with RSD of 2.6% (n = 5) were obtained, indicating the potential applicability of the method for the determination of trace levels of FT in environmental samples.

Simultaneous monitoring of humidity and chemical changes using quartz crystal microbalance sensors modified with nano-thin films.

PubMed

Selyanchyn, Roman; Korposh, Serhiy; Wakamatsu, Shunichi; Lee, Seung-Woo

2011-01-01

Quartz crystal microbalance (QCM) electrodes modified with nano-thin films were used to develop a system for measuring significant environment changes (smoke, humidity, hazardous material release). A layer-by-layer approach was used for the deposition of sensitive coatings with a nanometer thickness on the electrode surface. The QCM electrode was modified with self-assembled alternate layers of tetrakis-(4-sulfophenyl) porphine (TSPP) (or its manganese derivative, MnTSPP) and poly(diallyldimethylammonium chloride) (PDDA). The QCM sensors, which had been reported previously for humidity sensing purposes, revealing a high possibility to recognize significant environmental changes. Identifying of the origin of environmental change is possible via differential signal analysis of the obtained data. The sensors showed different responses to humidity changes, hazardous gas (ammonia) or cigarette smoke exposure. Even qualitative analysis is not yet available; it has been shown that ventilation triggers or alarms for monitoring smoke or hazardous material release can be built using the obtained result.

Voltammetric sensor for buzepide methiodide determination based on TiO2 nanoparticle-modified carbon paste electrode.

PubMed

Kalanur, Shankara S; Seetharamappa, Jaldappagari; Prashanth, S N

2010-07-01

In this work, we have prepared nano-material modified carbon paste electrode (CPE) for the sensing of an antidepressant, buzepide methiodide (BZP) by incorporating TiO2 nanoparticles in carbon paste matrix. Electrochemical studies indicated that the TiO2 nanoparticles efficiently increased the electron transfer kinetics between drug and the electrode. Compared with the nonmodified CPE, the TiO2-modified CPE greatly enhances the oxidation signal of BZP with negative shift in peak potential. Based on this, we have proposed a sensitive, rapid and convenient electrochemical method for the determination of BZP. Under the optimized conditions, the oxidation peak current of BZP is found to be proportional to its concentration in the range of 5 x 10(-8) to 5 x 10(-5)M with a detection limit of 8.2 x 10(-9)M. Finally, this sensing method was successfully applied for the determination of BZP in human blood serum and urine samples with good recoveries. 2010 Elsevier B.V. All rights reserved.

Photoelectrochemical NADH Regeneration using Pt-Modified p -GaAs Semiconductor Electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stufano, Paolo; Paris, Aubrey R.; Bocarsly, Andrew

Cofactor regeneration in enzymatic reductions is crucial for the application of enzymes to both biological and energy-related catalysis. Specifically, regenerating NADH from NAD + is of great interest, and using electrochemistry to achieve this end is considered a promising option. Here in this paper, we report the first example of photoelectrochemical NADH regeneration at the illuminated (λ >600 nm), metal-modified p-type semiconductor electrode Pt/p-GaAs. Although bare p-GaAs electrodes produce only enzymatically inactive NAD 2, NADH was produced at the illuminated Pt-modified p-GaAs surface. At low overpotential (–0.75 V vs. Ag/AgCl), Pt/p-GaAs exhibited a seven-fold greater Faradaic efficiency for the formationmore » of NADH than Pt alone, with reduced competition from the hydrogen evolution reaction. Improved Faradaic efficiency and low overpotential suggest the possible utility of Pt/p-GaAs in energy-related NADH-dependent enzymatic processes.« less

Honeycomb-like Porous Carbon-Cobalt Oxide Nanocomposite for High-Performance Enzymeless Glucose Sensor and Supercapacitor Applications.

PubMed

Madhu, Rajesh; Veeramani, Vediyappan; Chen, Shen-Ming; Manikandan, Arumugam; Lo, An-Ya; Chueh, Yu-Lun

2015-07-29

Herein, we report the preparation of Pongam seed shells-derived activated carbon and cobalt oxide (∼2-10 nm) nanocomposite (PSAC/Co3O4) by using a general and facile synthesis strategy. The as-synthesized PSAC/Co3O4 samples were characterized by a variety of physicochemical techniques. The PSAC/Co3O4-modified electrode is employed in two different applications such as high performance nonenzymatic glucose sensor and supercapacitor. Remarkably, the fabricated glucose sensor is exhibited an ultrahigh sensitivity of 34.2 mA mM(-1) cm(-2) with a very low detection limit (21 nM) and long-term durability. The PSAC/Co3O4 modified stainless steel electrode possesses an appreciable specific capacitance and remarkable long-term cycling stability. The obtained results suggest the as-synthesized PSAC/Co3O4 is more suitable for the nonenzymatic glucose sensor and supercapacitor applications outperforming the related carbon based modified electrodes, rendering practical industrial applications.

Functional interface of polymer modified graphite anode

NASA Astrophysics Data System (ADS)

Komaba, S.; Ozeki, T.; Okushi, K.

Graphite electrodes were modified by polyacrylic acid (PAA), polymethacrylic acid (PMA), and polyvinyl alcohol (PVA). Their electrochemical properties were examined in 1 mol dm -3 LiClO 4 ethylene carbonate:dimethyl carbonate (EC:DMC) and propylene carbonate (PC) solutions as an anode of lithium ion batteries. Generally, lithium ions hardly intercalate into graphite in the PC electrolyte due to a decomposition of the PC electrolyte at ca. 0.8 V vs. Li/Li +, and it results in the exfoliation of the graphene layers. However, the modified graphite electrodes with PAA, PMA, and PVA demonstrated the stable charge-discharge performance due to the reversible lithium intercalation not only in the EC:DMC but also in the PC electrolytes since the electrolyte decomposition and co-intercalation of solvent were successfully suppressed by the polymer modification. It is thought that these improvements were attributed to the interfacial function of the polymer layer on the graphite which interacted with the solvated lithium ions at the electrode interface.

Sensitive and Facile Electrochemiluminescent Immunoassay for Detecting Genetically Modified Rapeseed Based on Novel Carbon Nanoparticles.

PubMed

Gao, Hongfei; Wen, Luke; Wu, Yuhua; Yan, Xiaohong; Li, Jun; Li, Xiaofei; Fu, Zhifeng; Wu, Gang

2018-05-23

A highly sensitive electrochemiluminescent (ECL) immunoassay targeting PAT/ bar protein was facilely developed for genetically modified (GM) rapeseed detection using carbon nanoparticles (CNPs) originally prepared from printer toner. In this work, CNPs linked with antibody for PAT/ bar protein were used to modify a working electrode. After an immunoreaction between the PAT/ bar protein and its antibody, the immunocomplex formed on the electrode receptor region resulted in an inhibition of electron transfer between the electrode surface and the ECL substance, thus led to a decrease of ECL response. Under the optimal conditions, the ECL responses linearly decreased as the increase of the PAT/ bar protein concentration and the GM rapeseed RF3 content in the ranges of 0.10-10 ng/mL and 0.050-1.0%, with the limits of detection of 0.050 ng/mL and 0.020% (S/N = 3). These results open a facile, sensitive, and rapid approach for the safety control of agricultural GM rape.

Photoelectrochemical NADH Regeneration using Pt-Modified p -GaAs Semiconductor Electrodes

DOE PAGES

Stufano, Paolo; Paris, Aubrey R.; Bocarsly, Andrew

2017-02-22

Cofactor regeneration in enzymatic reductions is crucial for the application of enzymes to both biological and energy-related catalysis. Specifically, regenerating NADH from NAD + is of great interest, and using electrochemistry to achieve this end is considered a promising option. Here in this paper, we report the first example of photoelectrochemical NADH regeneration at the illuminated (λ >600 nm), metal-modified p-type semiconductor electrode Pt/p-GaAs. Although bare p-GaAs electrodes produce only enzymatically inactive NAD 2, NADH was produced at the illuminated Pt-modified p-GaAs surface. At low overpotential (–0.75 V vs. Ag/AgCl), Pt/p-GaAs exhibited a seven-fold greater Faradaic efficiency for the formationmore » of NADH than Pt alone, with reduced competition from the hydrogen evolution reaction. Improved Faradaic efficiency and low overpotential suggest the possible utility of Pt/p-GaAs in energy-related NADH-dependent enzymatic processes.« less

Nitric oxide-sensitive guanylyl cyclase is differentially regulated by nuclear and non-nuclear estrogen pathways in anterior pituitary gland.

PubMed

Cabilla, Jimena P; Nudler, Silvana I; Ronchetti, Sonia A; Quinteros, Fernanda A; Lasaga, Mercedes; Duvilanski, Beatriz H

2011-01-01

17β-estradiol (E2) regulates hormonal release as well as proliferation and cell death in the pituitary. The main nitric oxide receptor, nitric oxide sensitive- or soluble guanylyl cyclase (sGC), is a heterodimer composed of two subunits, α and β, that catalyses cGMP formation. α1β1 is the most abundant and widely expressed heterodimer, showing the greater activity. Previously we have shown that E2 decreased sGC activity but exerts opposite effects on sGC subunits increasing α1 and decreasing β1 mRNA and protein levels. In the present work we investigate the mechanisms by which E2 differentially regulates sGC subunits' expression on rat anterior pituitary gland. Experiments were performed on primary cultures of anterior pituitary cells from adult female Wistar rats at random stages of estrous cycle. After 6 h of E2 treatment, α1 mRNA and protein expression is increased while β1 levels are down-regulated. E2 effects on sGC expression are partially dependent on de novo transcription while de novo translation is fully required. E2 treatment decreased HuR mRNA stabilization factor and increased AUF1 p37 mRNA destabilization factor. E2-elicited β1 mRNA decrease correlates with a mRNA destabilization environment in the anterior pituitary gland. On the other hand, after 6 h of treatment, E2-BSA (1 nM) and E2-dendrimer conjugate (EDC, 1 nM) were unable to modify α1 or β1 mRNA levels, showing that nuclear receptor is involved in E2 actions. However, at earlier times (3 h), 1 nM EDC causes a transient decrease of α1 in a PI3k-dependent fashion. Our results show for the first time that E2 is able to exert opposite actions in the anterior pituitary gland, depending on the activation of classical or non-classical pathways. Thus, E2 can also modify sGC expression through membrane-initiated signals bringing to light a new point of regulation in NO/sGC pathway. © 2011 Cabilla et al.

Effect of Resin-modified Glass Ionomer Cement Dispensing/Mixing Methods on Mechanical Properties.

PubMed

Sulaiman, T A; Abdulmajeed, A A; Altitinchi, A; Ahmed, S N; Donovan, T E

2018-03-23

Resin-modified glass ionomer cements (RMGIs) are often used for luting indirect restorations. Hand-mixing traditional cements demands significant time and may be technique sensitive. Efforts have been made by manufacturers to introduce the same cement using different dispensing/mixing methods. It is not known what effects these changes may have on the mechanical properties of the dental cement. The purpose of this study was to evaluate the mechanical properties (diametral tensile strength [DTS], compressive strength [CS], and fracture toughness [FT]) of RMGIs with different dispensing/mixing systems. The RMGI specimens (n=14)-RelyX Luting (hand mix), RelyX Luting Plus (clicker-hand mix), RelyX Luting Plus (automix) (3M ESPE), GC Fuji PLUS (capsule-automix), and GC FujiCEM 2 (automix) (GC)-were prepared for each mechanical test and examined after thermocycling (n=7/subgroup) for 20,000 cycles to the following: DTS, CS (ISO 9917-1) and FT (ISO standard 6872; Single-edge V-notched beam method). Specimens were mounted and loaded with a universal testing machine until failure occurred. Two-/one-way analysis of variance followed by Tukey honestly significantly different post hoc test was used to analyze data for statistical significance ( p<0.05). The interaction effect of both dispensing/mixing method and thermocycling was significant only for the CS test of the GC group ( p<0.05). The different dispensing/mixing methods had no effect on the DTS of the tested cements. The CS of GC Fuji PLUS was significantly higher than that of the automix version ( p<0.05). The FT decreased significantly when switching from RelyX (hand mix) to RelyX Luting Plus (clicker-hand mix) and to RelyX Luting Plus (automix) ( p<0.05). Except in the case of the DTS of the GC group and the CS of GC Fuji PLUS, thermocycling had a significant effect reducing the mechanical properties of the RMGI cements ( p<0.05). Introducing alternative dispensing/mixing methods for mixing RMGIs to reduce time and technique sensitivity may affect mechanical properties and is brand dependent.

A non-enzymatic amperometric hydrogen peroxide sensor based on iron nanoparticles decorated reduced graphene oxide nanocomposite.

PubMed

Amanulla, Baishnisha; Palanisamy, Selvakumar; Chen, Shen-Ming; Velusamy, Vijayalakshmi; Chiu, Te-Wei; Chen, Tse-Wei; Ramaraj, Sayee Kannan

2017-02-01

A simple and facile green process was used for the synthesis of iron nanoparticles (FeNPs) decorated reduced graphene oxide (rGO) nanocomposite by using Ipomoea pes-tigridis leaf extract as a reducing and stabilizing agent. The as-prepared rGO/FeNPs nanocomposite was characterized by transmission electron microscopy, X-ray spectroscopy and Fourier transform infrared spectroscopy. The nanocomposite was further modified on the glassy carbon electrode and used for non-enzymatic sensing of hydrogen peroxide (H 2 O 2 ). Cyclic voltammetry results reveal that rGO/FeNPs nanocomposite has excellent electro-reduction behavior to H 2 O 2 when compared to the response of FeNPs and rGO modified electrodes. Furthermore, the nanocomposite modified electrode shows 9 and 6 folds enhanced reduction current response to H 2 O 2 than that of rGO and FeNPs modified electrodes. Amperometric method was further used to quantify the H 2 O 2 using rGO/FeNPs nanocomposite, and the response was linear over the concentration ranging from 0.1μM to 2.15mM. The detection limit and sensitivity of the sensor were estimated as 0.056μM and 0.2085μAμM -1 cm -2 , respectively. The fabricated sensor also utilized for detection of H 2 O 2 in the presence of potentially active interfering species, and found high selectivity towards H 2 O 2 . Copyright © 2016 Elsevier Inc. All rights reserved.

Evaluation of the degradation of acetaminophen by the filamentous fungus Scedosporium dehoogii using carbon-based modified electrodes.

PubMed

Mbokou, Serge Foukmeniok; Pontié, Maxime; Razafimandimby, Bienvenue; Bouchara, Jean-Philippe; Njanja, Evangéline; Tonle Kenfack, Ignas

2016-08-01

The nonpathogenic filamentous fungus Scedosporium dehoogii was used for the first time to study the electrochemical biodegradation of acetaminophen (APAP). A carbon fiber microelectrode (CFME) modified by nickel tetrasulfonated phthalocyanine (p-NiTSPc) and a carbon paste electrode (CPE) modified with coffee husks (CH) were prepared to follow the kinetics of APAP biodegradation. The electrochemical response of APAP at both electrodes was studied by cyclic voltammetry and square wave voltammetry. p-NiTSPc-CFME was suitable to measure high concentrations of APAP, whereas CH-CPE gave rise to high current densities but was subject to the passivation phenomenon. p-NiTSPc-CFME was then successfully applied as a sensor to describe the kinetics of APAP biodegradation: this was found to be of first order with a kinetics constant of 0.11 day(-1) (at 25 °C) and a half-life of 6.30 days. APAP biodegradation by the fungus did not lead to the formation of p-aminophenol (PAP) and hydroquinone (HQ) that are carcinogenic, mutagenic, and reprotoxic (CMR). Graphical Abstract The kinetics of APAP biodegradation, followed by a poly-nickel tetrasulfonated phtalocyanine modified carbon fiber microelectrode.

Carbon nanostructured films modified by metal nanoparticles supported on filtering membranes for electroanalysis.

PubMed

Paramo, Erica; Palmero, Susana; Heras, Aranzazu; Colina, Alvaro

2018-02-01

A novel methodology to prepare sensors based on carbon nanostructures electrodes modified by metal nanoparticles is proposed. As a proof of concept, a novel bismuth nanoparticle/carbon nanofiber (Bi-NPs/CNF) electrode and a carbon nanotube (CNT)/gold nanoparticle (Au-NPs) have been developed. Bi-NPs/CNF films were prepared by 1) filtering a dispersion of CNFs on a polytetrafluorethylene (PTFE) filter, and 2) filtering a dispersion of Bi-NPs chemically synthesized through this CNF/PTFE film. Next the electrode is prepared by sticking the Bi-NPs/CNF/PTFE film on a PET substrate. In this work, Bi-NPs/CNF ratio was optimized using a Cd 2+ solution as a probe sample. The Cd anodic stripping peak intensity, registered by differential pulse anodic stripping voltammetry (DPASV), is selected as target signal. The voltammograms registered for Cd stripping with this Bi-NPs/CNF/PTFE electrode showed well-defined and highly reproducible electrochemical. The optimized Bi-NPs/CNF electrode exhibits a Cd 2+ detection limit of 53.57 ppb. To demonstrate the utility and versatility of this methodology, single walled carbon nanotubes (SWCNTs) and gold nanoparticles (Au-NPs) were selected to prepare a completely different electrode. Thus, the new Au-NPs/SWCNT/PTFE electrode was tested with a multiresponse technique. In this case, UV/Vis absorption spectroelectrochemistry experiments were carried out for studying dopamine, demonstrating the good performance of the Au-NPs/SWCNT electrode developed. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation of non-specific binding suppression schemes for neutravidin and alkaline phosphatase at the surface of reticulated vitreous carbon electrodes.

PubMed

Shedge, Hemangi Y; Creager, Stephen E

2010-01-11

Non-specific binding (NSB) of high-molecular-weight proteins onto electrode surfaces can complicate the application of electroanalytical techniques to clinical and environmental research, particularly in biosensor applications. We present herein various strategies to modify the surface of reticulated vitreous carbon (RVC) electrodes to suppress non-specific binding of biomolecules onto its surface. Non-specific binding and specific binding (SB) of two enzyme conjugates, neutravidin-alkaline phosphatase (NA-ALP) and biotinylated alkaline phosphatase (B-ALP), and also neutravidin itself, were studied using hydroquinone diphosphate (HQDP) as an enzyme substrate for ALP inside the pores of RVC electrodes that had been subjected to various modification schemes. The extent of NSB and SB of these biomolecules inside RVC pores was assessed by measuring the initial rate of generation of an electroactive product, hydroquinone (HQ), of the enzyme-catalyzed reaction, using linear scan voltammetry (LSV) for HQ detection. Electrodes functionalized with phenylacetic acid and poly(ethylene glycol) (PEG) showed low NSB and high SB (when biotin capture ligands were included in the modification scheme) in comparison with unmodified electrodes and RVC electrodes modified in other ways. A simple sandwich bioassay for neutravidin was performed on the RVC electrode with the lowest NSB. A concentration detection limit of 52+/-2 ng mL(-1) and an absolute detection limit of 5.2+/-0.2 ng were achieved for neutravidin when this assay was performed using a 100 microL sample size.

Electrochemical Determination of Chlorpyrifos on a Nano-TiO₂Cellulose Acetate Composite Modified Glassy Carbon Electrode.

PubMed

Kumaravel, Ammasai; Chandrasekaran, Maruthai

2015-07-15

A rapid and simple method of determination of chlorpyrifos is important in environmental monitoring and quality control. Electrochemical methods for the determination of pesticides are fast, sensitive, reproducible, and cost-effective. The key factor in electrochemical methods is the choice of suitable electrode materials. The electrode materials should have good stability, reproducibility, more sensitivity, and easy method of preparation. Mercury-based electrodes have been widely used for the determination of chlorpyrifos. From an environmental point of view mercury cannot be used. In this study a biocompatible nano-TiO2/cellulose acetate modified glassy carbon electrode was prepared by a simple method and used for the electrochemical sensing of chlorpyrifos in aqueous methanolic solution. Electroanalytical techniques such as cyclic voltammetry, differential pulse voltammetry, and amperometry were used in this work. This electrode showed very good stability, reproducibility, and sensitivity. A well-defined peak was obtained for the reduction of chlorpyrifos in cyclic voltammetry and differential pulse voltammetry. A smooth noise-free current response was obtained in amperometric analysis. The peak current obtained was proportional to the concentration of chlorpyrifos and was used to determine the unknown concentration of chlorpyrifos in the samples. Analytical parameters such as LOD, LOQ, and linear range were estimated. Analysis of real samples was also carried out. The results were validated through HPLC. This composite electrode can be used as an alternative to mercury electrodes reported in the literature.

Rapid determination of methylmercury in fish and shellfish: method development

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hight, S.C.; Corcoran, M.T.

The AOAC official first action method for methylmercury in fish and shellfish was modified to provide more rapid determination. Methylmercury is isolated from homogenized, acetone-washed tissue by addition of HCl and extraction by toluene of the methylmercuric chloride produced. The extract is analyzed by electron capture gas chromatography (GC) on 5% DEGS-PS treated with mercuric chloride solution. The quantitation limit of the method is 0.25 ..mu..g Hg/g. Swordfish, shark, tuna, shrimp, clams, oysters, and NBS Research Material-50 (tuna) were analyzed for methylmercury by the AOAC official first action method. All products also were analyzed by the modified method and themore » AOAC official method for total Hg. In addition, selected extracts obtained with the modified method were analyzed by GC with Hg-selective, microwave-induced helium plasma detection. There was no significant different between the results for the various methods. Essentially all the Hg present (determined as total Hg) was in the organic form. Coefficients of variation from analyses by the modified method ranged from 1 to 7% for fish and shellfish containing methylmercury at levels of 0.50-2.30 ..mu..g Hg/g. The overall average recovery was 100.5%.« less

Laser patterning of platinum electrodes for safe neurostimulation

NASA Astrophysics Data System (ADS)

Green, R. A.; Matteucci, P. B.; Dodds, C. W. D.; Palmer, J.; Dueck, W. F.; Hassarati, R. T.; Byrnes-Preston, P. J.; Lovell, N. H.; Suaning, G. J.

2014-10-01

Objective. Laser surface modification of platinum (Pt) electrodes was investigated for use in neuroprosthetics. Surface modification was applied to increase the surface area of the electrode and improve its ability to transfer charge within safe electrochemical stimulation limits. Approach. Electrode arrays were laser micromachined to produce Pt electrodes with smooth surfaces, which were then modified with four laser patterning techniques to produce surface structures which were nanosecond patterned, square profile, triangular profile and roughened on the micron scale through structured laser interference patterning (SLIP). Improvements in charge transfer were shown through electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and biphasic stimulation at clinically relevant levels. A new method was investigated and validated which enabled the assessment of in vivo electrochemically safe charge injection limits. Main results. All of the modified surfaces provided electrical advantage over the smooth Pt. The SLIP surface provided the greatest benefit both in vitro and in vivo, and this surface was the only type which had injection limits above the threshold for neural stimulation, at a level shown to produce a response in the feline visual cortex when using an electrode array implanted in the suprachoroidal space of the eye. This surface was found to be stable when stimulated with more than 150 million clinically relevant pulses in physiological saline. Significance. Critical to the assessment of implant devices is accurate determination of safe usage limits in an in vivo environment. Laser patterning, in particular SLIP, is a superior technique for improving the performance of implant electrodes without altering the interfacial electrode chemistry through coating. Future work will require chronic in vivo assessment of these electrode patterns.

Spot-Welding Gun With Pivoting Twin-Collet Assembly

NASA Technical Reports Server (NTRS)

Nguyen, Francis; Simpson, Gareth; Hoult, William S.

1996-01-01

Modified spot-welding gun includes pivoting twin-collet assembly that holds two spot-welding electrodes. Designed to weld highly conductive (30 percent gold) brazing-alloy foils to thin nickel alloy workpieces; also suitable for other spot-welding applications compatible with two-electrode configuration.

Graphene/graphite paste electrode incorporated with molecularly imprinted polymer nanoparticles as a novel sensor for differential pulse voltammetry determination of fluoxetine.

PubMed

Alizadeh, Taher; Azizi, Sorour

2016-07-15

Molecularly imprinted polymer (MIP) nanoparticles including highly selective recognition sites for fluoxetine were synthesized, utilizing precipitation polymerization. Methacrylic acid and vinyl benzene were used as functional monomers. Ethylene glycol dimethacrylate was used as cross-linker agent. The obtained polymeric nanoparticles were incorporated with carbon paste electrode (CPE) in order to construct a fluoxetine selective sensor. The response of the MIP-CP electrode to fluoxetine was remarkably higher than the electrode, modified with the non-imprinted polymer, indicating the excellent efficiency of the MIP sites for target molecule recognition. It was found that the addition of a little amount of graphene, synthesized via modified hummer's method, to the MIP-CP resulted in considerable enhancement in the sensitivity of the electrode to fluoxetine. Also, the style of electrode components mixing, before carbon paste preparation, was demonstrated to be influential factor in the electrode response. Some parameters, affecting sensor response, were optimized and then a calibration curve was plotted. A dynamic linear range of 6×10(-9)-1.0×10(-7)molL(-1) was obtained. The detection limit of the sensor was calculated equal to 2.8×10(-9)molL(-1) (3Sb/m). This sensor was used successfully for fluoxetine determination in the spiked plasma samples as well as fluoxetine capsules. Copyright © 2016 Elsevier B.V. All rights reserved.

Development of a novel MWCNTs-triazene-modified carbon paste electrode for potentiometric assessment of Hg(II) in the aquatic environments.

PubMed

Mashhadizadeh, Mohammad Hossein; Ramezani, Soleyman; Rofouei, Mohammad Kazem

2015-02-01

In this approach, a new chemically modified carbon paste electrode was assembled for potentiometric assay of mercury(II) ion in the aqueous environments. Hereby, MWCNTs were used in the carbon paste composition to meliorate the electrical conductivity and sensitivity of the carbon paste owing to its exceptional physicochemical characteristics. Likewise, participation of the BEPT as a super-selective ionophore in the carbon paste composition boosted significantly the selectivity of the modified electrode towards Hg(II) ions over a wide concentration range of 4.0 × 10(-9)-2.2 × 10(-3) mol L(-1) with a lower detection limit of 3.1 × 10(-9) mol L(-1). Besides, Nernstian slope of the proposed sensor was 28.9(± 0.4)mV/decade over a pH range of 3.0-5.2 with potentiometric short response time of 10s. In the interim, by storing in the dark and cool dry place during non-usage period, the electrode can be used for at least 30 days without any momentous divergence of the potentiometric response. Eventually, to judge about its practical efficiency, the arranged sensor was utilized successfully as an indicator electrode for potentiometric titration of mercury(II) with standard solution of EDTA. As well, the quantitative analysis of mercury(II) ions in some aqueous samples with sensible accuracy and precision was satisfactorily performed. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and characterisation of Co-Co(OH)2 composite anode material on Cu current collector for energy storage devices

NASA Astrophysics Data System (ADS)

Yavuz, Abdulcabbar; Yakup Hacıibrahimoğlu, M.; Bedir, Metin

2017-04-01

A Co-Co(OH)2 modified electrode on inexpensive Cu substrate was synthesized at room temperature and demonstrated to be a promising anode material for energy storage devices. A modified Co film was obtained potentiostatically and was then potentiodynamically treated with KOH solution to form Co(OH)2. Co-Co(OH)2 coatings were obtained and were dominated by Co(OH)2 at the oxidized side, whereas Co dominant Co-Co(OH)2 occurred at the reduced side (-1.1 V). As OH- ions were able to diffuse into (out of) the film during oxidation (reduction) and did not react with the Cu current collector, the Co-Co(OH)2 electrode can be used as an anode material in energy storage devices. Although the specific capacitance of the electrodes varied depending on thickness, the redox reaction between the modified electrode and KOH electrolyte remained the same consisting of a surface-controlled and diffusion-controlled mechanism which had a desirable fast charge and discharge property. Capacity values remained constant after 250 cycles as the film evolved. Overall capacity retention was 84% for the film after 450 scans. A specific capacitance of 549 F g-1 was obtained for the Co-Co(OH)2 composite electrode in 6 M KOH at a scan rate of 5 mV s-1 and 73% of capacitance was retained when the scan rate was increased to 100 mV s-1.

Ultra-sensitive film sensor based on Al2O3-Au nanoparticles supported on PDDA-functionalized graphene for the determination of acetaminophen.

PubMed

Li, Jianbo; Sun, Weiyan; Wang, Xiaojiao; Duan, Huimin; Wang, Yanhui; Sun, Yuanling; Ding, Chaofan; Luo, Chuannan

2016-08-01

An electrochemical sensor of acetaminophen based on poly(diallyldimethylammonium chloride) (PDDA)-functionalized reduced graphene-loaded Al2O3-Au nanoparticles coated onto glassy carbon electrode (Al2O3-Au/PDDA/reduced graphene oxide (rGO)/glass carbon electrode (GCE)) were prepared by layer self-assembly technique. The as-prepared electrode-modified materials were characterized by scanning electron microscopy, X-ray powder diffraction, and Fourier transform infrared spectroscopy. The electrocatalytic performances of Al2O3-Au/PDDA/rGO-modified glassy carbon electrode toward the acetaminophen were investigated by cyclic voltammetry and differential pulse voltammetry. The modified electrodes of graphene oxide (GO)/GCE, PDDA/rGO/GCE, and Al2O3-Au/PDDA/rGO/GCE were constructed for comparison and learning the catalytic mechanism. The research showed Al2O3-Au/PDDA/rGO/GCE having good electrochemical performance, attributing to the synergetic effect that comes from the special nanocomposite structure and physicochemical properties of Al2O3-Au nanoparticles and graphene. A low detection limit of 6 nM (S/N = 3) and a wide linear detection range from 0.02 to 200 μM (R (2) = 0.9970) was obtained. The preparation of sensor was successfully applied for the detection of acetaminophen in commercial pharmaceutical pills. Graphical abstract Schematic diagram of synthesis of Al2O3-Au/PDDA/rGO/GCE.

The Cu-MOF-199/single-walled carbon nanotubes modified electrode for simultaneous determination of hydroquinone and catechol with extended linear ranges and lower detection limits.

PubMed

Zhou, Jian; Li, Xi; Yang, Linlin; Yan, Songlin; Wang, Mengmeng; Cheng, Dan; Chen, Qi; Dong, Yulin; Liu, Peng; Cai, Weiquan; Zhang, Chaocan

2015-10-29

A novel electrochemical sensor based on Cu-MOF-199 [Cu-MOF-199 = Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylicacid)] and SWCNTs (single-walled carbon nanotubes) was fabricated for the simultaneous determination of hydroquinone (HQ) and catechol (CT). The modification procedure was carried out through casting SWCNTs on the bare glassy carbon electrode (GCE) and followed by the electrodeposition of Cu-MOF-199 on the SWCNTs modified electrode. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were performed to characterize the electrochemical performance and surface characteristics of the as-prepared sensor. The composite electrode exhibited an excellent electrocatalytic activity with increased electrochemical signals towards the oxidation of HQ and CT, owing to the synergistic effect of SWCNTs and Cu-MOF-199. Under the optimized condition, the linear response range were from 0.1 to 1453 μmol L(-1) (RHQ = 0.9999) for HQ and 0.1-1150 μmol L(-1) (RCT = 0.9990) for CT. The detection limits for HQ and CT were as low as 0.08 and 0.1 μmol L(-1), respectively. Moreover, the modified electrode presented the good reproducibility and the excellent anti-interference performance. The analytical performance of the developed sensor for the simultaneous detection of HQ and CT had been evaluated in practical samples with satisfying results. Copyright © 2015 Elsevier B.V. All rights reserved.

Screening of inorganic gases released from firework-rockets by a gas chromatography/whistle-accelerometer method.

PubMed

Chen, Kuan-Fu; Wu, Hui-Hsin; Lin, Chien-Hung; Lin, Cheng-Huang

2013-08-30

The use of an accelerometer for detecting inorganic gases in gas chromatography (GC) is described. A milli-whistle was connected to the outlet of the GC capillary and was used instead of a classical GC detector. When the GC carrier gases and the sample gases pass through the milli-whistle, a sound is produced, leading to vibrational changes, which can be recorded using an accelerometer. Inorganic gases, including SO2, N2 and CO2, which are released from traditional Chinese firework-rockets at relatively high levels as the result of burning the propellant and explosive material inside could be rapidly determined using the GC/whistle-accelerometer system. The method described herein is safe, the instrumentation is compact and has potential to be modified so as to be portable for use in the field. It also can be used in conjunction with FID (flame ionization detector) or TCD (thermal conductivity detector), in which either no response for FID (CO2, N2, NO2, SO2, etc.) or helium gas is needed for TCD, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrochemical Determination of Food Preservative Nitrite with Gold Nanoparticles/p-Aminothiophenol-Modified Gold Electrode.

PubMed

Üzer, Ayşem; Sağlam, Şener; Can, Ziya; Erçağ, Erol; Apak, Reşat

2016-08-02

Due to the negative impact of nitrate and nitrite on human health, their presence exceeding acceptable levels is not desired in foodstuffs. Thus, nitrite determination at low concentrations is a major challenge in electroanalytical chemistry, which can be achieved by fast, cheap, and safe electrochemical sensors. In this work, the working electrode (Au) was functionalized with p-aminothiophenol (p-ATP) and modified with gold nanoparticles (Au-NPs) to manufacture the final (Au/p-ATP-Aunano) electrode in a two-step procedure. In the first step, p-ATP was electropolymerized on the electrode surface to obtain a polyaminothiophenol (PATP) coating. In the second step, Au/p-ATP-Aunano working electrode was prepared by coating the surface with the use of HAuCl₄ solution and cyclic voltammetry. Determination of aqueous nitrite samples was performed with the proposed electrode (Au/p-ATP-Aunano) using square wave voltammetry (SWV) in pH 4 buffer medium. Characteristic peak potential of nitrite samples was 0.76 V, and linear calibration curves of current intensity versus concentration was linear in the range of 0.5-50 mg·L(-1) nitrite with a limit of detection (LOD) of 0.12 mg·L(-1). Alternatively, nitrite in sausage samples could be colorimetrically determined with high sensitivity by means of p-ATP‒modified gold nanoparticles (AuNPs) and naphthylethylene diamine as coupling agents for azo-dye formation due to enhanced charge-transfer interactions with the AuNPs surface. The slopes of the calibration lines in pure NO₂(-) solution and in sausage sample solution, to which different concentrations of NO₂(-) standards were added, were not significantly different from each other, confirming the robustness and interference tolerance of the method. The proposed voltammetric sensing method was validated against the colorimetric nanosensing method in sausage samples.

An electrochemical sensor for homocysteine detection using gold nanoparticle incorporated reduced graphene oxide.

PubMed

Rajaram, Rajendran; Mathiyarasu, Jayaraman

2018-05-30

In this work, we report a methodology for the quantification of Homocysteine (HcySH) at neutral pH (pH-7.0) using Au nanoparticles incorporated reduced graphene oxide (AuNP/rGO/GCE) modified glassy carbon electrode. The modified electrode was characterized using SEM and XRD techniques. The electrode exhibited a typical behavior against the standard redox probe [Fe(CN) 6 ] 3-/4- and resulted in 0.06 V peak to peak potential value. The modified electrode exhibited electrocatalytic activity towards electrochemical biosensing of HcySH, which is established using voltammetric studies. HcySH oxidation peak potential is observed at 0.12 V on AuNP/rGO/GCE which is 0.7 V cathodic than bare glassy carbon electrode (0.82 V). The large peak potential shift observed is reasoned as the interaction of SH group of HcySH with the gold nanoparticles and the electrocatalytic property of reduced graphene oxide that enhances the electrochemical detection at reduced overpotential. Further, successive addition of HcySH showed a linear increment in the sensitivity within the concentration range of 2-14 mM. From an amperometric protocol, the limit of detection is found as 6.9 μM with a sensitivity of 14.8 nA/μM. From a set of cyclic voltammetric measurements, it is observed that the electrode produces a linear signal on the concentration of HcySH in the presence of hydrogen peroxide. Thus it can be concluded that the matrix can detect HcySH even in the presence of hydrogen peroxide. Copyright © 2018 Elsevier B.V. All rights reserved.

Partially Reduced Graphene Oxide Modified Tetrahedral Amorphous Carbon Thin-Film Electrodes as a Platform for Nanomolar Detection of Dopamine

DOE PAGES

Wester, Niklas; Sainio, Sami; Palomäki, Tommi; ...

2017-03-16

Here, we present for the first time tetrahedral amorphous carbon (ta-C)—a partially reduced graphene oxide (PRGO) hybrid electrode nanomaterial platform for electrochemical sensing of dopamine (DA). Graphene oxide was synthesized with the modified Hummer’s method. Before modification of ta-C by drop casting, partial reduction of the GO was carried out to improve electrochemical properties and adhesion to the ta-C thin film. A facile nitric acid treatment that slightly reoxidized the surface and modified the surface chemistry was subsequently performed to further improve the electrochemical properties of the electrodes. The largest relative increase was seen in carboxyl groups. The HNO 3more » treatment increased the sensitivity toward DA and AA and resulted in a cathodic shift in the oxidation of AA. The fabricated hybrid electrodes were characterized with scanning electron microscopy (SEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and electrochemical impedance spectroscopy (EIS). Moreover, compared to the plain ta-C electrode the hybrid electrode was shown to exhibit superior sensitivity and selectivity toward DA in the presence of ascorbic acid (AA), enabling simultaneous sensing of AA and DA close to the physiological concentrations by cyclic voltammetry (CV) and by differential pulse voltammetry (DPV). Two linear ranges of 0–1 μM and 1–100 μM and a detection limit (S/N = 3.3) of 2.6 nM for DA were determined by means of cyclic voltammetry. Thus, the current work provides a fully CMOS-compatible carbon based hybrid nanomaterial that shows potential for in vivo measurements of DA.« less

Effects of adsorbed pyridine derivatives and ultrathin atomic-layer-deposited alumina coatings on the conduction band-edge energy of TiO2 and on redox-shuttle-derived dark currents.

PubMed

Katz, Michael J; Vermeer, Michael J D; Farha, Omar K; Pellin, Michael J; Hupp, Joseph T

2013-01-15

Both the adsorption of t-butylpyridine and the atomic-layer deposition of ultrathin conformal coatings of insulators (such as alumina) are known to boost open-circuit photovoltages substantially for dye-sensitized solar cells. One attractive interpretation is that these modifiers significantly shift the conduction-edge energy of the electrode, thereby shifting the onset potential for dark current arising from the interception of injected electrons by solution-phase redox shuttle components such as Co(phenanthroline)(3)(3+) and triiodide. For standard, high-area, nanoporous photoelectrodes, band-edge energies are difficult to measure directly. In contrast, for flat electrodes they are readily accessible from Mott-Schottky analyses of impedance data. Using such electrodes (specifically TiO(2)), we find that neither organic nor inorganic electrode-surface modifiers shift the conduction-band-edge energy sufficiently to account fully for the beneficial effects on electrode behavior (i.e., the suppression of dark current). Additional experiments reveal that the efficacy of ultrathin coatings of Al(2)O(3) arises chiefly from the passivation of redox-catalytic surface states. In contrast, adsorbed t-butylpyridine appears to suppress dark currents mainly by physically blocking access of shuttle molecules to the electrode surface. Studies with other derivatives of pyridine, including sterically and/or electronically diverse derivatives, show that heterocycle adsorption and the concomitant suppression of dark current does not require the coordination of surface Ti(IV) or Al(III) atoms. Notably, the favorable (i.e., negative) shifts in onset potential for the flow of dark current engendered by organic and inorganic surface modifiers are additive. Furthermore, they appear to be largely insensitive to the identity of shuttle molecules.