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Sample records for direct electrochemistry etude

  1. Electrochemistry

    SciTech Connect

    Rieger, P.H.

    1987-01-01

    In my view, Rieger's Electrochemistry falls in the category of excellent textbooks. It is very well written and presents the more challenging concepts of electrochemistry logically and lucidly. This book would be an excellent choice for use in an advanced undergraduate or first-year graduate-level course in general electrochemistry. The emphasis is on the physical aspects of electrochemistry, perhaps reflecting the author's primary interest in mechanistic studies. For a course emphasizing the analytical aspects of electrochemistry, considerable supplementation would be required and other, more appropriate textbooks are available.

  2. Construction and direct electrochemistry of orientation controlled laccase electrode

    SciTech Connect

    Li, Ying; Zhang, Jiwei; Huang, Xirong; Wang, Tianhong

    2014-03-28

    Highlights: • A recombinant laccase with Cys-6×His tag at the N or C terminus was generated. • Orientation controlled laccase electrodes were constructed via self assembly. • The electrochemical behavior of laccase electrodes was orientation dependent. • The C terminus tagged laccase was better for bioelectrocatalytic reduction of O{sub 2}. - Abstract: A laccase has multiple redox centres. Chemisorption of laccases on a gold electrode through a polypeptide tag introduced at the protein surface provides an isotropic orientation of laccases on the Au surface, which allows the orientation dependent study of the direct electrochemistry of laccase. In this paper, using genetic engineering technology, two forms of recombinant laccase which has Cys-6×His tag at the N or C terminus were generated. Via the Au-S linkage, the recombinant laccase was assembled orientationally on gold electrode. A direct electron transfer and a bioelectrocatalytic activity toward oxygen reduction were observed on the two orientation controlled laccase electrodes, but their electrochemical behaviors were found to be quite different. The orientation of laccase on the gold electrode affects both the electron transfer pathway and the electron transfer efficiency of O{sub 2} reduction. The present study is helpful not only to the in-depth understanding of the direct electrochemistry of laccase, but also to the development of laccase-based biofuel cells.

  3. Construction and direct electrochemistry of orientation controlled laccase electrode.

    PubMed

    Li, Ying; Zhang, Jiwei; Huang, Xirong; Wang, Tianhong

    2014-03-28

    A laccase has multiple redox centres. Chemisorption of laccases on a gold electrode through a polypeptide tag introduced at the protein surface provides an isotropic orientation of laccases on the Au surface, which allows the orientation dependent study of the direct electrochemistry of laccase. In this paper, using genetic engineering technology, two forms of recombinant laccase which has Cys-6×His tag at the N or C terminus were generated. Via the Au-S linkage, the recombinant laccase was assembled orientationally on gold electrode. A direct electron transfer and a bioelectrocatalytic activity toward oxygen reduction were observed on the two orientation controlled laccase electrodes, but their electrochemical behaviors were found to be quite different. The orientation of laccase on the gold electrode affects both the electron transfer pathway and the electron transfer efficiency of O2 reduction. The present study is helpful not only to the in-depth understanding of the direct electrochemistry of laccase, but also to the development of laccase-based biofuel cells. Copyright © 2014 Elsevier Inc. All rights reserved.

  4. A review on direct electrochemistry of catalase for electrochemical sensors.

    PubMed

    Prakash, Periasamy Arun; Yogeswaran, Umasankar; Chen, Shen-Ming

    2009-01-01

    Catalase (CAT) is a heme enzyme with a Fe((III/II)) prosthetic group at its redox centre. CAT is present in almost all aerobic living organisms, where it catalyzes the disproportionation of H(2)O(2) into oxygen and water without forming free radicals. In order to study this catalytic mechanism in detail, the direct electrochemistry of CAT has been investigated at various modified electrode surfaces with and without nanomaterials. The results show that CAT immobilized on nanomaterial modified electrodes shows excellent catalytic activity, high sensitivity and the lowest detection limit for H(2)O(2) determination. In the presence of nanomaterials, the direct electron transfer between the heme group of the enzyme and the electrode surface improved significantly. Moreover, the immobilized CAT is highly biocompatible and remains extremely stable within the nanomaterial matrices. This review discusses about the versatile approaches carried out in CAT immobilization for direct electrochemistry and electrochemical sensor development aimed as efficient H(2)O(2) determination. The benefits of immobilizing CAT in nanomaterial matrices have also been highlighted.

  5. Chitosan-Promoted Direct Electrochemistry of Human Sulfite Oxidase.

    PubMed

    Kalimuthu, Palraj; Belaidi, Abdel A; Schwarz, Guenter; Bernhardt, Paul V

    2017-10-05

    Direct electrochemistry of human sulfite oxidase (HSO) has been achieved on carboxylate-terminated self-assembled monolayers cast on a Au working electrode in the presence of the promoter chitosan. The modified electrode facilitates a well-defined nonturnover redox response from the heme cofactor (Fe(III/II)) in 750 mM Tris, MOPS, and bicine buffer solutions. The formal redox potential of the nonturnover response varies slightly depending on the nature of the thiol monolayer on the Au electrode. Upon addition of sulfite to the cell a pronounced catalytic current from HSO-facilitated sulfite oxidation is observed. The measured catalytic rate constant (kcat) is around 0.2 s(-1) (compared with 26 s(-1) obtained from solution assays), which indicates that interaction of the enzyme with the electrode lowers overall catalysis although native behavior is retained in terms of substrate concentration dependence, pH dependence, and inhibition effects. In contrast, no catalytic activity is observed when HSO is confined to amine-terminated thiol monolayers although well-defined noncatalytic responses from the heme cofactor are still observed. These differences are linked to flexibility of HSO, which can switch between active and inactive conformations, and also competitive ion exchange processes at the electrode surface involving the enzyme and substrate.

  6. Direct electrochemistry and electrocatalysis of a glucose oxidase-functionalized bioconjugate as a trace label for ultrasensitive detection of thrombin.

    PubMed

    Bai, Lijuan; Yuan, Ruo; Chai, Yaqin; Yuan, Yali; Wang, Yan; Xie, Shunbi

    2012-11-18

    For the first time, a glucose oxidase-functionalized bioconjugate was prepared and served as a new trace label through its direct electrochemistry and electrocatalysis in a sandwich-type electrochemical aptasensor for ultrasensitive detection of thrombin.

  7. Direct electrochemistry of Penicillium chrysogenum catalase adsorbed on spectroscopic graphite.

    PubMed

    Dimcheva, Nina; Horozova, Elena

    2013-04-01

    The voltammetric studies of Penicillium chrysogenum catalase (PcCAT) adsorbed on spectroscopic graphite, showed direct electron transfer (DET) between its active site and the electrode surface. Analogous tests performed with the commercially available bovine catalase revealed that mammalian enzyme is much less efficient in the DET process. Both catalases were found capable to catalyse the electrooxidation of phenol, but differed in the specifics of catalytic action. At an applied potential of 0.45V the non-linear regression showed the kinetics of the bioelectrochemical oxidation catalysed by the PcCAT obeyed the Hill equation with a binding constant K=0.034±0.002 M(2) (Hill's coefficient n=2.097±0.083, R(2)=0.997), whilst the catalytic action of the bovine catalase was described by the Michaelis-Menten kinetic model with the following parameters: V(max,app)=7.780±0.509 μA, and K(M,app)=0.068±0.070 mol L(-1). The performance of the electrode reaction was affected by the electrode potential, the pH, and temperature. Based on the effect of pH and temperature on the electrode response in presence of phenol a tentative reaction pathway of its bioelectrocatalytic oxidation has been hypothesised. The possible application of these findings in biosensing phenol up to concentration 30 mM at pHs below 7 and in absence of oxidising agents (oxygen or H(2)O(2)) was considered.

  8. Direct electrochemistry of GOD on nitrogen-doped porous carbon and its biosensing

    NASA Astrophysics Data System (ADS)

    Sun, Min; Liu, Hongyu; Chen, Shouhui; Song, Yonghai; Wang, Li

    2014-11-01

    Nitrogen-doped porous carbon (N-DPC) was prepared via a simple and effective method and was characterized by X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, N2 adsorption-desorption isotherms and scanning electron microscopy. The results showed that the N-DPC with two type reticular porosities in an average diameter of 10-100 nm has a large specific surface area, which is favorable to immobilize the redox proteins for constructing biosensors. Direct electrochemistry of glucose oxidase (GOD) on the N-DPC-modified electrode was investigated. UV-vis spectroscopy showed that GOD retained its catalytic activity in the N-DPC film. Electrochemical results indicated that the modified electrode exhibited effective direct electron transfer. It demonstrated that such N-DPC could provide a good matrix for direct electrochemistry of enzymes. A novel biosensor was developed by entrapping GOD in the N-DPC-modified electrode for glucose detection and showed a stable, rapid, and reproducible electrocatalytic response, a high sensitivity, a wide linear range and a low detection limit. Moreover, the biosensor can be applied in practical analysis and exhibit good reproducibility and long-term stability.

  9. 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.

  10. Direct electrochemistry of xanthine oxidase at a gold electrode modified with single-wall carbon nanotubes.

    PubMed

    Wang, Liang; Yuan, Zhuobin

    2004-04-01

    The direct electrochemistry of xanthine oxidase (XOD) was accomplished at a gold electrode modified with single-wall carbon nanotubes (SWNTs). A pair of well-defined redox peaks was obtained for XOD with the reduction peak potential at -0.478 V and a peak potential separation of 28 mV at pH 7.0. Both FT-IR spectra and the dependence of the reduction peak current on the scan rate revealed that XOD adsorbed onto the SWNT surfaces. The redox wave corresponds to the redox center of the flavin adenine dinucleotide (FAD) of the XOD adsorbate. Compared to other types of carbonaceous electrode materials, the electron transfer rate of XOD redox reaction was greatly enhanced at the SWNT-modified electrode. The peak potential was shown to be pH dependent. Spectral methods verified that the attachment of XOD onto SWNTs does not perturb the XOD conformations drastically.

  11. Reagentless amperometric immunosensors based on direct electrochemistry of horseradish peroxidase for determination of carcinoma antigen-125.

    PubMed

    Dai, Zong; Yan, Feng; Chen, Jin; Ju, Huangxian

    2003-10-15

    A novel strategy for immunoassay and the preparation of reagentless immunosensors was proposed. This strategy was based on the immobilization of antigen and the direct electrochemistry of horseradish peroxidase (HRP) that was labeled to an antibody. A reagentless immunosensor for carcinoma antigen-125 (CA 125) determination was developed. The immunosensor was prepared by immobilizing CA 125 with titania sol-gel on a glassy carbon electrode by the vapor deposition method. The incubation of the immunosensor in phosphate buffer solution (PBS) including HRP-labeled CA 125 antibody led to the formation of a HRP-modified surface. The immobilized HRP displayed its direct electrochemistry with a rate constant of 3.04 +/- 1.21 s(-1). With a competition mechanism, a differential pulse voltammetric determination method for CA 125 was established by the peak current decrease of the immobilized HRP. The current decrease resulted from the competitive binding of the CA 125 in sample solution and the immobilized CA 125 to the limited amount of HRP-labeled CA 125 antibody. Under optimal conditions, the current decrease was proportional to CA 125 concentration ranging from 2 to 14 units mL(-1) with a detection limit of 1.29 units mL(-1) at a current decrease by 10%. The CA 125 immunosensor showed good accuracy and acceptable precision and fabrication reproducibility with intraassay CVs of 8.7 and 5.5% at 8 and 14 units mL(-1) CA 125 concentrations, respectively, and interassay CV of 19.8% at 8 units mL(-1). The storage stability was acceptable in a pH 7.0 PBS at 4 degrees C for 15 days. The proposed method provided a new promising platform for clinical immunoassay.

  12. ZnO/Cu nanocomposite: a platform for direct electrochemistry of enzymes and biosensing applications.

    PubMed

    Yang, Chi; Xu, Chunxiang; Wang, Xuemei

    2012-03-06

    Unique structured nanomaterials can facilitate the direct electron transfer between redox proteins and the electrodes. Here, in situ directed growth on an electrode of a ZnO/Cu nanocomposite was prepared by a simple corrosion approach, which enables robust mechanical adhesion and electrical contact between the nanostructured ZnO and the electrodes. This is great help to realize the direct electron transfer between the electrode surface and the redox protein. SEM images demonstrate that the morphology of the ZnO/Cu nanocomposite has a large specific surface area, which is favorable to immobilize the biomolecules and construct biosensors. Using glucose oxidase (GOx) as a model, this ZnO/Cu nanocomposite is employed for immobilization of GOx and the construction of the glucose biosensor. Direct electron transfer of GOx is achieved at ZnO/Cu nanocomposite with a high heterogeneous electron transfer rate constant of 0.67 ± 0.06 s(-1). Such ZnO/Cu nanocomposite provides a good matrix for direct electrochemistry of enzymes and mediator-free enzymatic biosensors.

  13. Polymerized ionic liquid-wrapped carbon nanotubes: the promising composites for direct electrochemistry and biosensing of redox protein.

    PubMed

    Xiao, Chunhui; Chu, Xiaochen; Wu, Bohua; Pang, Haili; Zhang, Xiaohua; Chen, Jinhua

    2010-03-15

    Polymerized ionic liquid-wrapped carbon nanotubes (PIL-CNTs) were firstly designed for direct electrochemistry and biosensing of redox proteins. The CNTs were coated successfully with polymerized ionic liquid (PIL) layer, as verified by transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR) spectroscopy. The PIL-CNTs were dispersed better in water and showed superior electrocatalysis toward O(2) and H(2)O(2) comparing to pristine CNTs and the mixture of IL monomer and CNTs. With glucose oxidase (GOD) as a protein model, the direct electrochemistry of the redox protein was investigated on the PIL-CNTs modified glassy carbon (GC) electrode and excellent direct electrochemical performance of GOD molecules was observed. The proposed biosensor (GOD/PIL-CNTs/GC electrode) displayed good analytical performance for glucose with linear response up to 6mM, response sensitivity of 0.853 microA mM(-1), good stability and selectivity.

  14. 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.

  15. Fabrication of graphene-platinum nanocomposite for the direct electrochemistry and electrocatalysis of myoglobin.

    PubMed

    Sun, Wei; Li, Linfang; Lei, Bingxin; Li, Tongtong; Ju, Xiaomei; Wang, Xiuzheng; Li, Guangjiu; Sun, Zhenfan

    2013-05-01

    In this paper a platinum (Pt) nanoparticle decorated graphene (GR) nanosheet was synthesized and used for the investigation on direct electrochemistry of myoglobin (Mb). By integrating GR-Pt nanocomposite with Mb on the surface of carbon ionic liquid electrode (CILE), a new electrochemical biosensor was fabricated. UV-Vis absorption and FT-IR spectra indicated that Mb remained its native structure in the nanocomposite film. Electrochemical behaviors of Nafion/Mb-GR-Pt/CILE were investigated with a pair of well-defined redox peak appeared, which indicated that direct electron transfer of Mb was realized on the underlying electrode with the usage of the GR-Pt nanocomposite. The fabricated electrode showed good electrocatalytic activity to the reduction of trichloroacetic acid in the linear range from 0.9 to 9.0 mmol/L with the detection limit as 0.32 mmol/L (3σ), which showed potential application for fabricating novel electrochemical biosensors and bioelectronic devices. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. Direct Electrochemistry of Hemoglobin at a Graphene Gold Nanoparticle Composite Film for Nitric Oxide Biosensing

    PubMed Central

    Xu, Miao-Qing; Wu, Jian-Feng; Zhao, Guang-Chao

    2013-01-01

    A simple two-step method was employed for preparing nano-sized gold nanoparticles-graphene composite to construct a GNPs-GR-SDS modified electrode. Hemoglobin (Hb) was successfully immobilized on the surface of a basal plane graphite (BPG) electrode through a simple dropping technique. Direct electrochemistry and electrocatalysis of the hemoglobin-modified electrode was investigated. The as-prepared composites showed an obvious promotion of the direct electro-transfer between hemoglobin and the electrode. A couple of well-defined and quasi-reversible Hb CV peaks can be observed in a phosphate buffer solution (pH 7.0). The separation of anodic and cathodic peak potentials is 81 mV, indicating a fast electron transfer reaction. The experimental results also clarified that the immobilized Hb retained its biological activity for the catalysis toward NO. The biosensor showed high sensitivity and fast response upon the addition of NO, under the conditions of pH 7.0, potential -0.82 V. The time to reach the stable-state current was less than 3 s, and the linear response range of NO was 0.72-7.92 μM, with a correlation coefficient of 0.9991. PMID:23748173

  17. Glucose oxidase-graphene-chitosan modified electrode for direct electrochemistry and glucose sensing

    SciTech Connect

    Kang, Xinhuang; Wang, Jun; Wu, Hong; Aksay, Ilhan A.; Liu, Jun; Lin, Yuehe

    2009-11-01

    Direct electrochemistry of a glucose oxidase (GOD)/graphene/chitosan nanocomposite was studied. The immobilized enzyme retains its bioactivity, exhibits a surface confined, reversible two-proton and two-electron transfer reaction, and has good stability, activity and a fast heterogeneous electron transfer rate with the rate constant (ks) of 2.83 s-1. A much higher enzyme loading (1.12 × 10-9 mol/cm2) is obtained as compared to the bare glass carbon surface. This GOD/graphene/chitosan nanocomposite film can be used for sensitive detection of glucose. The biosensor exhibits a wider linearity range from 0.08 mM to 12 mM glucose with a detection limit of 0.02 mM and much higher sensitivity (37.93 μA mM-1 cm-2) as compared with other nanostructured supports. The excellent performance of the biosensor is attributed to large surface-to-volume ratio and high conductivity of graphene, and good biocompatibility of chitosan, which enhances the enzyme absorption and promotes direct electron transfer between redox enzymes and the surface of electrodes.

  18. Carbon nanodots-chitosan composite film: a platform for protein immobilization, direct electrochemistry and bioelectrocatalysis.

    PubMed

    Sheng, Meili; Gao, Yue; Sun, Junyong; Gao, Feng

    2014-08-15

    A novel composite film based on carbon nanodots (CNDs) and chitosan was readily prepared and used as immobilization matrix to entrap a heme protein, hemoglobin (Hb) for direct electrochemistry and bioelectrocatalysis. A modified electrode was obtained by casting Hb-CNDs-chitosan composites on the glassy carbon (GC) electrode surface. Spectroscopic and electrochemical studies showed that Hb entrapped in the composite film remained in its native structures, and CNDs in the film can greatly facilitate DET between the protein and the GC electrode. The electron-transfer kinetics of Hb in composite film was qualitatively evaluated by using the Marcus theory, and the apparent heterogeneous electron-transfer rate constant (ks) was estimated to be 2.39(±0.03)s(-1) with Laviron equations. The modified electrode showed excellent electrocatalytic behavior to the substrate, hydrogen peroxide (H2O2). The linear current response for H2O2 was from 1×10(-6) to 1.18×10(-4)M with a detection limit of 0.27(±0.02)μM at the signal-to-noise ratio of 3, and the apparent Michaelis-Menten constant was 0.067(±0.02)mM. These important features of CNDs-chitosan film have implied to be a promising platform for elaborating bioelectrochemical devices such as biosensors and biofuel cells.

  19. Direct electrochemistry and electrocatalysis of myoglobin immobilized on zirconia/multi-walled carbon nanotube nanocomposite

    SciTech Connect

    Liang, Ruping; Deng, Minqiang; Cui, Sanguan; Chen, Hong; Qiu, Jianding

    2010-12-15

    Zirconia/multi-walled carbon nanotube (ZrO{sub 2}/MWCNT) nanocomposite was prepared by hydrothermal treatment of MWCNTs in ZrOCl{sub 2}.8H{sub 2}O aqueous solution. The morphology and structure of the synthesized ZrO{sub 2}/MWCNT nanocomposite were characterized by transmission electron microscopy and X-ray diffraction analysis. It was found that ZrO{sub 2} nanoparticles homogeneously distributed on the sidewall of MWCNTs. Myoglobin (Mb), as a model protein to investigate the nanocomposite, was immobilized on ZrO{sub 2}/MWCNT nanocomposite. Ultraviolet-visible spectroscopy and electrochemical measurements showed that the nanocomposite could retain the bioactivity of the immobilized Mb to a large extent. The Mb immobilized in the composite showed excellent direct electrochemistry and electrocatalytic activity to the reduction of hydrogen peroxide (H{sub 2}O{sub 2}). The linear response range of the biosensor to H{sub 2}O{sub 2} concentration was from 1.0 to 116.0 {mu}M with the limit of detection of 0.53 {mu}M (S/N = 3). The ZrO{sub 2}/MWCNT nanocomposite provided a good biocompatible matrix for protein immobilization and biosensors preparation.

  20. Direct electrochemistry of dopamine on gold-Agaricus bisporus laccase enzyme electrode: characterization and quantitative detection.

    PubMed

    Shervedani, Reza Karimi; Amini, Akbar

    2012-04-01

    Direct electrochemistry of a new laccase enzyme immobilized on gold and its application as a biosensor for dopamine (DA) are investigated by voltammetry and electrochemical impedance spectroscopy. The sensor demonstrated a redox adsorption behavior with E(0') = + 180 mV vs. Ag/AgCl for immobilized Agaricus bisporus laccase (LacAB) enzyme. The MPA platform was assembled on Au with and without utilization of ultrasounds. Excellent results were obtained by using the enzyme electrode fabricated based on MPA assembled with sonication. The LacAB immobilized in this condition showed a large electrocatalytic activity for oxidation of DA. Accordingly, a third-generation (mediator free) biosensor was constructed for DA. The DA concentration could be measured in the linear range of 0.5 to 13.0 and 47.0 to 430.0 μmol L(-1) with correlation coefficients of 0.999 and 0.989, respectively, and a detection limit of 29.0 nmol L(-1). The biosensor was successfully tested for determination of DA in human blood plasma and pharmaceutical samples. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. Direct electrochemistry and electrocatalysis of hemoglobin in nafion/carbon nanochip film on glassy carbon electrode.

    PubMed

    George, Sini; Lee, Hian Kee

    2009-11-26

    The use of heat treated carbon nanofibers, known as carbon nanochips (CNCs) for the studies of the direct electrochemistry and electrocatalytic properties of heme proteins, is demonstrated. A glassy carbon electrode (GCE) was modified with CNCs, and hemoglobin (Hb) was immobilized on the modified electrode surface by casting a film of Hb. Nafion was employed to fix the CNCs and Hb tightly on the surface of the GCE. The modified electrode was characterized by scanning electron microscopy. Ultraviolet-visible and Fourier transform infrared spectroscopy showed that Hb immobilized in the CNC film remained in its native structure. Electrochemical impedance spectroscopy and cyclic voltammetry (CV) were employed for electrochemical studies. The results showed that the presence of CNCs in the film can greatly enhance the electrochemical response of Hb. A pair of well-defined reversible CV peaks was observed, and the formal potential of the heme Fe(III)/Fe(II) redox couple was found to be -253 mV [vs Ag/AgCl (saturated KCl)]. The apparent heterogeneous electron-transfer rate constant (k(s)) was estimated as 2.54 s(-1). The modified electrode showed excellent electrocatalytic behavior to hydrogen peroxide (H(2)O(2)), trichloroacetic acid, and sodium nitrite. H(2)O(2) had a linear current response from 0.5 to 30 microM (R(2) = 0.9997; n = 5) with a detection limit of 0.05 microM when the signal-to-noise ratio was 3 and the apparent Michaelis-Menten constant (K(m)(app)) was 21.55 microM. These values suggest that CNCs are the best matrix described so far for the development of biosensors, far superior to untreated carbon nanofibers. The direct immobilization of proteins onto the surface of CNCs is shown to be a highly efficient method for the development of a new class of very sensitive, stable, and reproducible electrochemical biosensors.

  2. Core-shell structured Ag@C for direct electrochemistry and hydrogen peroxide biosensor applications.

    PubMed

    Mao, Shuxian; Long, Yumei; Li, Weifeng; Tu, Yifeng; Deng, Anping

    2013-10-15

    Ag@C core-shell nano-composites have been prepared by a simple one-step hydrothermal method and are further explored for protein immobilization and bio-sensing. The electrochemical behavior of immobilized horseradish peroxidase (HRP) on Ag@C modified indium-tin-oxide (ITO) electrode and its application as H₂O₂ sensor are investigated. Electrochemical and UV-vis spectroscopic measurements demonstrated that Ag@C nano-composites provide excellent matrixes for the adsorption of HRP and the entrapped HRP retains its bioactivities. It is found that on the HRP-Ag@C/ITO electrode, HRP exhibited a fast electron transfer process and good electrocatalytic reduction toward H₂O₂. Under optimum experimental conditions the biosensor linearly responds to H₂O₂ concentration in the range of 5.0×10⁻⁷-1.4×10⁻⁴ M with a detection limit of 2.0×10⁻⁷ M (S/N=3). The apparent Michaelis-Menten constant (K(app)(M)) of the biosensor is calculated to be 3.75×10⁻⁵ M, suggesting high enzymatic activity and affinity toward H₂O₂. In addition, the HRP-Ag@C/ITO bio-electrode shows good reproducibility and long-term stability. Thus, the core-shell structured Ag@C is an attractive material for application in the fabrication of biosensors due to its direct electrochemistry and functionalized surface for efficient immobilization of bio-molecules.

  3. Direct electrochemistry of alcohol oxidase using multiwalled carbon nanotube as electroactive matrix for biosensor application.

    PubMed

    Das, Madhuri; Goswami, Pranab

    2013-02-01

    Rapid detection of alcohol is important in clinical diagnosis and fermentation industry. An octameric alcohol oxidase (AOx) (Mr 675 kDa) from Pichia pastoris, immobilized on multiwalled carbon nanotubes-Nafion® (MWCNT-Nf) matrix and encapsulated with polyethylenimine (PEI) on gold electrode (AuE), showed a redox peak at 0.21V (vs. Ag/AgCl electrode at pH 7.5) for oxidation of alcohol. The electron transfer rate constant and surface coverage of the immobilized AOx were 1.69±0.15 s⁻¹ and 2.43×10⁻¹² mol cm⁻², respectively. Studies on response and kinetics of Au-MWCNT-Nf-AOx-PEI bioelectrodes for alcohol showed a linear response in the range of 8 μM-42 μM, response time of 55 s for steady state current, and detection limit of 5 μM. The bioelectrode retains ~90% of the original response even after four weeks when stored in potassium phosphate buffer pH 7.5 at 4 °C. The fabricated bioelectrode was found to exclude interference caused by the common electroactive species such as ascorbic acid, uric acid, lactic acid, glucose and urea. The bioelectrode also showed reliable response characteristics in blood serum samples. The findings of the investigation have established the direct electrochemistry of the AOx protein and its potential biosensor application for quantitative detection of alcohol in blood serum. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Direct electrochemistry and intramolecular electron transfer of ascorbate oxidase confined on L-cysteine self-assembled gold electrode.

    PubMed

    Patil, Bhushan; Kobayashi, Yoshiki; Fujikawa, Shigenori; Okajima, Takeyoshi; Mao, Lanqun; Ohsaka, Takeo

    2014-02-01

    A direct electrochemistry and intramolecular electron transfer of multicopper oxidases are of a great importance for the fabrication of these enzyme-based bioelectrochemical-devices. Ascorbate oxidase from Acremonium sp. (ASOM) has been successfully immobilized via a chemisorptive interaction on the l-cysteine self-assembled monolayer modified gold electrode (cys-SAM/AuE). Thermodynamics and kinetics of adsorption of ASOM on the cys-SAM/AuE were studied using cyclic voltammetry. A well-defined redox wave centered at 166±3mV (vs. Ag│AgCl│KCl(sat.)) was observed in 5.0mM phosphate buffer solution (pH7.0) at the fabricated ASOM electrode, abbreviated as ASOM/cys-SAM/AuE, confirming a direct electrochemistry, i.e., a direct electron transfer (DET) between ASOM and cys-SAM/AuE. The direct electrochemistry of ASOM was further confirmed by taking into account the chemical oxidation of ascorbic acid (AA) by O2 via an intramolecular electron transfer in the ASOM as well as the electrocatalytic oxidation of AA at the ASOM/cys-SAM/AuE. Thermodynamics and kinetics of the adsorption of ASOM on the cys-SAM/AuE have been elaborated along with its direct electron transfer at the modified electrodes on the basis of its intramolecular electron transfer and electrocatalytic activity towards ascorbic acid oxidation and O2 reduction. ASOM saturated surface area was obtained as 2.41×10(-11)molcm(-2) with the apparent adsorption coefficient of 1.63×10(6)Lmol(-1). The ASOM confined on the cys-SAM/AuE possesses its essential enzymatic function. © 2013.

  5. Bipolar electrochemistry.

    PubMed

    Fosdick, Stephen E; Knust, Kyle N; Scida, Karen; Crooks, Richard M

    2013-09-27

    A bipolar electrode (BPE) is an electrically conductive material that promotes electrochemical reactions at its extremities (poles) even in the absence of a direct ohmic contact. More specifically, when sufficient voltage is applied to an electrolyte solution in which a BPE is immersed, the potential difference between the BPE and the solution drives oxidation and reduction reactions. Because no direct electrical connection is required to activate redox reactions, large arrays of electrodes can be controlled with just a single DC power supply or even a battery. The wireless aspect of BPEs also makes it possible to electrosynthesize and screen novel materials for a wide variety of applications. Finally, bipolar electrochemistry enables mobile electrodes, dubbed microswimmers, that are able to move freely in solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A glucose biosensor based on direct electrochemistry of glucose oxidase immobilized on nitrogen-doped carbon nanotubes.

    PubMed

    Deng, Shengyuan; Jian, Guoqiang; Lei, Jianping; Hu, Zheng; Ju, Huangxian

    2009-10-15

    A novel biosensor for glucose was prepared by immobilizing glucose oxidase (GOx) on nitrogen-doped carbon nanotubes (CNx-MWNTs) modified electrode. The CNx-MWNTs membrane showed an excellent electrocatalytic activity toward the reduction of O(2) due to its diatomic side-on adsorption on CNx-MWNTs. The nitrogen doping accelerated the electron transfer from electrode surface to the immobilized GOx, leading to the direct electrochemistry of GOx. The biofunctional surface showed good biocompatibility, excellent electron-conductive network and large surface-to-volume ratio, which were characterized by scanning electron microscopy, contact angle and electrochemical impedance technique. The direct electron transfer of immobilized GOx led to stable amperometric biosensing for glucose with a linear range from 0.02 to 1.02 mM and a detection limit of 0.01 mM (S/N=3). These results indicated that CNx-MWNTs are good candidate material for construction of the third-generation enzyme biosensors based on the direct electrochemistry of immobilized enzymes.

  7. Hydrogen peroxide biosensor based on the direct electrochemistry of myoglobin immobilized on silver nanoparticles doped carbon nanotubes film.

    PubMed

    Liu, Chuan-Yin; Hu, Ji-Ming

    2009-03-15

    A novel H(2)O(2) biosensor has been fabricated based on the direct electrochemistry and electrocatalysis of myoglobin (Mb) immobilized on silver nanoparticles doped carbon nanotubes film with hybrid sol-gel techniques. A pair of redox peaks with peak separation of 160 mV and formal potential of -0.295V was observed at this composite film, corresponding to the direct electrochemistry of Mb. The heterogeneous rate constant was estimated to be 0.41s(-1). Under optimum conditions, the amperometric determination of H(2)O(2) was performed with a linear range of 2.0 x 10(-6)-1.2 x 10(-3)molL(-1) and a detection limit of 3.6 x 10(-7)mol/L (S/N=3). The Michealis-Menten constant was also estimated to be 1.62mmolL(-1). The proposed biosensor showed favorable reproducibility, stability, selectivity and accuracy, and has been used to determine H(2)O(2) in real samples with favorable recoveries.

  8. Direct electrochemistry and electrocatalytic behavior of hemoglobin entrapped in Ag@C nanocables/gold nanoparticles nanocomposites film.

    PubMed

    Hu, Xiao-Wei; Mao, Chang-Jie; Song, Ji-Ming; Niu, He-Lin; Zhang, Sheng-Yi; Cui, Rong-Jing

    2012-10-01

    Direct electrochemistry of hemoglobin (Hb) was successfully fabricated by immobilizing Hb on the nanocomposites containing of Ag@C nanocables and Au nanoparticles (AuNPs) modified glassy carbon electrode (GCE). The immobilized Hb retained its biological activity and shown high catalytic activities to the reduction of H2O2 by circular dicroism (CD) spectrum, fourier transform infrared (FT-IR) spectrum and cyclic voltammetry (CV). Experimental conditions such as scan rate and pH Value were studied and optimized. The results indicated that the resulting biosensor are linear to the concentrations of H2O2 in the ranges of 6.67 x 10(-7)-2.40 x 10(5) M, and the detection limit is 2.02 x 10(-7) M. The electrochemical biosensor has also high stability and good reproducibility.

  9. Achieving direct electrochemistry of glucose oxidase by one step electrochemical reduction of graphene oxide and its use in glucose sensing.

    PubMed

    Shamsipur, Mojtaba; Tabrizi, Mahmoud Amouzadeh

    2014-12-01

    In this paper, the direct electrochemistry of glucose oxidase (GOD) was accomplished at a glassy carbon electrode modified with electrochemically reduced graphene oxide/sodium dodecyl sulfate (GCE/ERGO/SDS). A pair of reversible peaks is exhibited on GCE/ERGO/SDS/GOD by cyclic voltammetry. The peak-to-peak potential separation of immobilized GOD is 28 mV in 0.1 M phosphate buffer solution (pH7.0) with a scan rate of 50 mV/s. The average surface coverage is 2.62×10(-10) mol cm(-2). The resulting biosensor exhibited a good response to glucose with linear range from 1 to 8 mM (R(2)=0.9878), good reproducibility and detection limit of 40.8 μM. The results from the biosensor were similar (±5%) to those obtained from the clinical analyzer.

  10. Catalytic Protein Film Electrochemistry Provides a Direct Measure of the Tetrathionate/Thiosulfate Reduction Potential.

    PubMed

    Kurth, Julia M; Dahl, Christiane; Butt, Julea N

    2015-10-21

    The tetrathionate/thiosulfate interconversion is a two-electron process: S4O6(2-) + 2 e(-) ↔ 2 S2O3(2-). Both transformations can support bacterial growth since S2O3(2-) provides an energy source, while S4O6(2-) serves as respiratory electron acceptor. Interest in the corresponding S2O3(2-) oxidation also arises from its widespread use in volumetric analysis of oxidizing agents and bleach neutralization during water treatment. Here we report protein film electrochemistry that defines the reduction potential of the S4O6(2-)/S2O3(2-) couple. The relevant interconversion is not reversible at inert electrodes. However, facile reduction of S4O6(2-) to S2O3(2-) and the reverse reaction are catalyzed by enzymes of the thiosulfate dehydrogenase, TsdA, family adsorbed on graphite electrodes. Zero-current potentials measured with different enzymes, at three pH values, and multiple S4O6(2-) and S2O3(2-) concentrations together with the relevant Nernst equation resolved the tetrathionate/thiosulfate reduction potential as +198 ± 4 mV versus SHE. This potential lies in the ∼250 mV window encompassing previously reported values calculated from parameters including the free energy of formation. However, the value is considerably more positive than widely used in discussions of bacterial bioenergetics. As a consequence anaerobic respiration by tetrathionate reduction is likely to be more prevalent than presently thought in tetrathionate-containing environments such as marine sediments and the human gut.

  11. 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.

  12. 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.

  13. Electrochemical quartz crystal microbalance studies on enzymatic specific activity and direct electrochemistry of immobilized glucose oxidase in the presence of sodium dodecyl benzene sulfonate and multiwalled carbon nanotubes.

    PubMed

    Su, Yuhua; Xie, Qingji; Chen, Chao; Zhang, Qingfang; Ma, Ming; Yao, Shouzhuo

    2008-01-01

    The electrochemical quartz crystal microbalance (EQCM) technique was utilized to monitor in situ the adsorption of glucose oxidase (GOD) and the mixture of GOD and sodium dodecyl benzene sulfonate (SDBS) onto Au electrodes with and without modification of multiwalled carbon nanotubes (MWCNTs) or SDBS/MWCNTs composite, and the relationship between enzymatic specific activity (ESA) and direct electrochemistry of the immobilized GOD was quantitatively evaluated for the first time. Compared with the bare gold electrode at which a little GOD was adsorbed and the direct electrochemistry of the adsorbed GOD was negligible, the amount and electroactivity of adsorbed GOD were greatly enhanced when the GOD was mixed with SDBS and then adsorbed onto the SDBS/MWCNTs modified Au electrode. However, the ESA of the adsorbed GOD was fiercely decreased to only 16.1% of the value obtained on the bare gold electrode, and the portion of adsorbed GOD showing electrochemical activity exhibited very low enzymatic activity, demonstrating that the electroactivity and ESA of immobilized GOD responded oppositely to the presence of MWCNTs and SDBS. The ESA results obtained from the EQCM method were well supported by conventional UV-vis spectrophotometry. The direct electrochemistry of redox proteins including enzymes as a function of their biological activities is an important concern in biotechnology, and this work may have presented a new and useful protocol to quantitatively evaluate both the electroactivity and ESA of trace immobilized enzymes, which is expected to find wider applications in biocatalysis and biosensing fields.

  14. Direct electrochemistry of cytochrome c immobilized on titanium nitride/multi-walled carbon nanotube composite for amperometric nitrite biosensor.

    PubMed

    Haldorai, Yuvaraj; Hwang, Seung-Kyu; Gopalan, Anantha-Iyengar; Huh, Yun Suk; Han, Young-Kyu; Voit, Walter; Sai-Anand, Gopalan; Lee, Kwang-Pill

    2016-05-15

    In this report, titanium nitride (TiN) nanoparticles decorated multi-walled carbon nanotube (MWCNTs) nanocomposite is fabricated via a two-step process. These two steps involve the decoration of titanium dioxide nanoparticles onto the MWCNTs surface and a subsequent thermal nitridation. Transmission electron microscopy shows that TiN nanoparticles with a mean diameter of ≤ 20 nm are homogeneously dispersed onto the MWCNTs surface. Direct electrochemistry and electrocatalysis of cytochrome c immobilized on the MWCNTs-TiN composite modified on a glassy carbon electrode for nitrite sensing are investigated. Under optimum conditions, the current response is linear to its concentration from 1 µM to 2000 µM with a sensitivity of 121.5 µA µM(-1)cm(-2) and a low detection limit of 0.0014 µM. The proposed electrode shows good reproducibility and long-term stability. The applicability of the as-prepared biosensor is validated by the successful detection of nitrite in tap and sea water samples.

  15. Fullerene-nitrogen doped carbon nanotubes for the direct electrochemistry of hemoglobin and its application in biosensing.

    PubMed

    Sheng, Qinglin; Liu, Ruixiao; Zheng, Jianbin

    2013-12-01

    The direct electrochemistry of hemoglobin (Hb) immobilized by a fullerene-nitrogen doped carbon nanotubes and chitosan (C60-NCNTs/CHIT) composite matrix is demonstrated. The cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the modified electrode. In the deaerated buffer solution, the cyclic voltammogram of the Hb/C60-NCNTs/CHIT composite film modified electrode showed a pair of well-behaved redox peaks with the E°'=-0.335 (± 0.3) V (vs. SCE). The redox peaks are assigned to the redox reaction of Hb(Fe(III)/Fe(II)) and confirm the effective immobilization of Hb on the composite film. The large value of ks = 1.8 (± 0.2)s(-1) suggests that the immobilized Hb achieved a relative fast electron transfer process. The fast electron transfer interaction between protein and electrode surface suggested that the C60-NCNTs/CHIT composite film may mimic some physiological process and further elucidate the relationship between protein structures and biological functions. Moreover, the resulting electrode exhibited excellent electrocatalytic ability towards the reduction of hydrogen peroxide (H2O2) with the linear dynamic range of 2.0-225.0 μM. The linear regression equation was Ip/μA=7.35 (± 0.08)+0.438 (± 0.007)C/μM with the correlation coefficient of 0.9993. The detection limit was estimated at about 1 μM (S/N=3). The sensitivity was 438.0 (± 2.5) μA mM(-1). It is expected that the method presented here can not only be easily extended to other redox enzymes or proteins, but also be used as an electrochemical sensing devices for the determination of H2O2 in cell extracts or urine. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Sol-gel derived silica/chitosan/Fe3O4 nanocomposite for direct electrochemistry and hydrogen peroxide biosensing

    NASA Astrophysics Data System (ADS)

    Satvekar, R. K.; Rohiwal, S. S.; Tiwari, A. P.; Raut, A. V.; Tiwale, B. M.; Pawar, S. H.

    2015-01-01

    A novel strategy to fabricate hydrogen peroxide third generation biosensor has been developed from sol-gel of silica/chitosan (SC) organic-inorganic hybrid material assimilated with iron oxide magnetic nanoparticles (Fe3O4). The large surface area of Fe3O4 and porous morphology of the SC composite facilitates a high loading of horseradish peroxidase (HRP). Moreover, the entrapped enzyme preserves its conformation and biofunctionality. The fabrication of hydrogen peroxide biosensor has been carried out by drop casting of the SC/F/HRP nanocomposite on glassy carbon electrode (GCE) for study of direct electrochemistry. The x-ray diffraction (XRD) pattern and transmission electron microscopy (TEM) confirms the phase purity and particle size of as-synthesized Fe3O4 nanoparticles, respectively. The nanocomposite was characterized by UV-vis spectroscopy, fluorescence spectroscopy and Fourier transform infrared (FTIR) for the characteristic structure and conformation of enzyme. The surface topographies of the nanocomposite thin films were investigated by scanning electron microscopy (SEM). Dynamic light scattering (DLS) was used to determine the particle size distribution. The electrostatic interactions of the SC composite with Fe3O4 nanoparticles were studied by the zeta potential measurement. Electrochemical impedance spectroscopy (EIS) of the SC/F/HRP/GCE electrode displays Fe3O4 nanoparticles as an excellent candidate for electron transfer. The SC/F/HRP/GCE exhibited a pair of well-defined quasi reversible cyclic voltammetry peaks due to the redox couple of HRP-heme Fe (III)/Fe (II) in pH 7.0 potassium phosphate buffer. The biosensor was employed to detect H2O2 with linear range of 5 μM to 40 μM and detection limit of 5 μM. The sensor displays excellent selectivity, sensitivity, good reproducibility and long term stability.

  17. Carbon nanotubes-nanoflake-like SnS2 nanocomposite for direct electrochemistry of glucose oxidase and glucose sensing.

    PubMed

    Li, Juan; Yang, Zhanjun; Tang, Yan; Zhang, Yongcai; Hu, Xiaoya

    2013-03-15

    Multi-walled carbon nanotubes (MWCNTs)-nanoflake-like SnS(2) nanocomposite were designed for immobilization of glucose oxidase (GOx). The direct electrochemistry of GOx and glucose sensing at MWCNTs-SnS(2) modified glassy carbon electrode were studied. Compared with single MWCNTs or SnS(2), the MWCNTs-SnS(2) film has larger surface area and provides a more favorable microenvironment for facilitating the electron transfer between enzyme and electrode surface. The properties of GOx/MWCNTs-SnS(2) were examined by scanning electron microscopy, UV-vis spectroscopy, Fourier transform infrared spectroscopy and cyclic voltammetry. The immobilized enzyme on MWCNTs-SnS(2) composite film retained its native structure and bioactivity and showed a surface controlled, reversible two-proton and two-electron transfer reaction with a apparent electron transfer rate constant of 3.96 s(-1). The constructed glucose biosensor exhibits wider linear range from 2.0×10(-5) M to 1.95×10(-3) M, much lower detection limit of 4.0×10(-6) M at signal-to-noise of 3 and higher sensitivity of 21.65 mA M(-1) cm(-2) than our previous nanoflake-like SnS(2)-based glucose sensor. The proposed biosensor has excellent selectivity, good reproducibility, and acceptable operational stability and can be successfully applied in the reagentless glucose sensing at -0.43 V. This MWCNTs-SnS(2) composite provides a new avenue for immobilizing proteins and fabricating excellent biosensors.

  18. Direct Electrochemistry of Cytochrome bo Oxidase at a series of Gold Nanoparticles-Modified Electrodes.

    PubMed

    Melin, Frederic; Meyer, Thomas; Lankiang, Styven; Choi, Sylvia K; Gennis, Robert B; Blanck, Christian; Schmutz, Marc; Hellwig, Petra

    2013-01-01

    New membrane-protein based electrodes were prepared incorporating cytochrome bo(3) from E. coli and gold nanoparticles. Direct electron transfer between the electrode and the immobilized enzymes was achieved, resulting in an electrocatalytic activity in presence of O(2). The size of the gold nanoparticles was shown to be important and smaller particles were shown to reduce the overpotential of the process.

  19. Direct Electrochemistry and Electrocatalysis of Hemoglobin at Mesoporous Carbon Modified Electrode

    PubMed Central

    Pei, Supeng; Qu, Song; Zhang, Yongming

    2010-01-01

    The novel highly ordered mesoporous carbon (known as FDU-15), prepared by the organic-organic self-assembly method was been used for first time for the immobilization of hemoglobin (Hb) and its bioelectrochemical properties were studied. The resulting Hb/FDU-15 film provided a favorable microenvironment for Hb to perform direct electron transfers at the electrode. The immobilized Hb also displayed its good electrocatalytic activity for the reduction of hydrogen peroxide. The results demonstrate that mesoporous carbon FDU-15 can improve the Hb loading with retention of its bioactivity and greatly promote the direct electron transfer, which can be attributed to its high specific surface area, uniform ordered porous structure, suitable pore size and biocompatibility. Our present study may provide an alternative way for the construction of nanostructure biofunctional surfaces and pave the way for its application to biosensors. PMID:22205867

  20. Direct Electrochemistry of Cytochrome bo3 Oxidase at a series of Gold Nanoparticles-Modified Electrodes

    PubMed Central

    Melin, Frederic; Meyer, Thomas; Lankiang, Styven; Choi, Sylvia K.; Gennis, Robert B; Blanck, Christian; Schmutz, Marc; Hellwig, Petra

    2012-01-01

    New membrane-protein based electrodes were prepared incorporating cytochrome bo3 from E. coli and gold nanoparticles. Direct electron transfer between the electrode and the immobilized enzymes was achieved, resulting in an electrocatalytic activity in presence of O2. The size of the gold nanoparticles was shown to be important and smaller particles were shown to reduce the overpotential of the process. PMID:23335854

  1. Improved direct electrochemistry for proteins adsorbed on a UV/ozone-treated carbon nanofiber electrode.

    PubMed

    Xue, Qiang; Kato, Dai; Kamata, Tomoyuki; Guo, Qiaohui; You, Tianyan; Niwa, Osamu

    2013-01-01

    We studied the direct electron transfer (DET) of proteins on a carbon nanofiber (CNF) modified carbon film electrode by employing the one-step UV/ozone treatment of CNF. This treatment changed the CNF surface from hydrophobic to hydrophilic because a sufficient quantity of oxygen functional groups was introduced onto the CNF surface. Furthermore, this simple approach increased both the effective surface area and the number of edge-plane defect sites. As a result, the reversibility of redox species, such as ferrocyanide and dopamine, was greatly improved on the treated electrode surface. We obtained on efficient DET of bilirubin oxidase (BOD) and cytochrome c (cyt c) at the treated CNF electrode, which exhibited 38 (for BOD) and 6 (for cyt c) times higher than that at untreated CNF modified electrode. These results indicate that the combination of nanostructured carbon and this UV/ozone treatment process can efficiently create a functionalized surface for the electron transfer of proteins.

  2. Addressable Direct-Write Nanoscale Filament Formation and Dissolution by Nanoparticle-Mediated Bipolar Electrochemistry.

    PubMed

    Crouch, Garrison M; Han, Donghoon; Fullerton-Shirey, Susan K; Go, David B; Bohn, Paul W

    2017-05-23

    Nanoscale conductive filaments, usually associated with resistive memory or memristor technology, may also be used for chemical sensing and nanophotonic applications; however, realistic implementation of the technology requires precise knowledge of the conditions that control the formation and dissolution of filaments. Here we describe and characterize an addressable direct-write nanoelectrochemical approach to achieve repeatable formation/dissolution of Ag filaments across a ∼100 nm poly(ethylene oxide) (PEO) film containing either Ag(+) alone or Ag(+) together with 50 nm Ag-nanoparticles acting as bipolar electrodes. Using a conductive AFM tip, formation occurs when the PEO film is subjected to a forward bias, and dissolution occurs under reverse bias. Formation-dissolution kinetics were studied for three film compositions: Ag|PEO-Ag(+), Ag|poly(ethylene glycol) monolayer-PEO-Ag(+), and Ag|poly(ethylene glycol) monolayer-PEO-Ag(+)/Ag-nanoparticle. Statistical analysis shows that the distribution of formation times exhibits Gaussian behavior, and the fastest average initial formation time occurs for the Ag|PEO-Ag(+) system. In contrast, formation in the presence of Ag nanoparticles likely proceeds by a noncontact bipolar electrochemical mechanism, exhibiting the slowest initial filament formation. Dissolution times are log-normal for all three systems, and repeated reformation of filaments from previously formed structures is characterized by rapid regrowth. The direct-write bipolar electrochemical deposition/dissolution strategy developed here presents an approach to reconfigurable, noncontact in situ wiring of nanoparticle arrays-thereby enabling applications where actively controlled connectivity of nanoparticle arrays is used to manipulate nanoelectronic and nanophotonic behavior. The system further allows for facile manipulation of experimental conditions while simultaneously characterizing surface conditions and filament formation/dissolution kinetics.

  3. Layer-by-layer assembly of functionalized reduced graphene oxide for direct electrochemistry and glucose detection.

    PubMed

    Mascagni, Daniela Branco Tavares; Miyazaki, Celina Massumi; da Cruz, Nilson Cristino; de Moraes, Marli Leite; Riul, Antonio; Ferreira, Marystela

    2016-11-01

    We report an electrochemical glucose biosensor made with layer-by-layer (LbL) films of functionalized reduced graphene oxide (rGO) and glucose oxidase (GOx). The LbL assembly using positively and negatively charged rGO multilayers represents a simple approach to develop enzymatic biosensors. The electron transport properties of graphene were combined with the specificity provided by the enzyme. rGO was obtained and functionalized using chemical methods, being positively charged with poly(diallyldimethylammonium chloride) to form GPDDA, and negatively charged with poly(styrene sulfonate) to form GPSS. Stable aqueous dispersions of GPDDA and GPSS are easily obtained, enabling the growth of LbL films on various solid supports. The use of graphene in the immobilization of GOx promoted Direct Electron Transfer, which was evaluated by Cyclic Voltammetry. Amperometric measurements indicated a detection limit of 13.4μmol·L(-1) and sensitivity of 2.47μA·cm(-2)·mmol(-1)·L for glucose with the (GPDDA/GPSS)1/(GPDDA/GOx)2 architecture, whose thickness was 19.80±0.28nm, as determined by Surface Plasmon Resonance (SPR). The sensor may be useful for clinical analysis since glucose could be detected even in the presence of typical interfering agents and in real samples of a lactose-free milk and an electrolyte solution to prevent dehydration.

  4. Direct proteins electrochemistry based on ionic liquid mediated carbon nanotube modified glassy carbon electrode.

    PubMed

    Zhao, Qiang; Zhan, Dongping; Ma, Hongyang; Zhang, Meiqin; Zhao, Yifang; Jing, Ping; Zhu, Zhiwei; Wan, Xinhua; Shao, Yuanhua; Zhuang, Qiankun

    2005-01-01

    A novel glassy carbon electrode modified by a gel containing multi-walled carbon nanotubes (MWNTs) and ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF6) is reported. The gel is formed by grinding of MWNTs and BMIPF6. Such gel is then coated on the surface of a glassy carbon electrode. We have employed scanning electron microscopy, Fourier transform infrared spectrometry (FTIR) and cyclic voltammetry to characterize the modified electrode. The direct electron transfers of hemoglobin and catalase on the modified electrode have been observed and studied in detail electrochemically. Hemoglobin is verified to be adsorbed on the modified electrode with the retention of conformation, which has been proved by microscopic FTIR. The electrochemical response of the adsorbed hemoglobin on the modified electrode is very stable, and shows repeated changes in the different pH solutions. It also has shown electrocatalysis to the reduction of oxygen and trichloroacetic acid. Catalase adsorbed on the gel modified electrode still keep activity to hydrogen peroxide. This work provides a simple and easy approach to construct biosensors based on the carbon nanotubes and ionic liquids.

  5. Multifunctional carbon nanotubes for direct electrochemistry of glucose oxidase and glucose bioassay.

    PubMed

    Wang, Yinling; Liu, Lin; Li, Maoguo; Xu, Shudong; Gao, Feng

    2011-12-15

    Polydopamine (Pdop) has recently been shown to adsorb to a wide variety of surfaces and serves as an adhesion layer to immobilize biological molecules. In this work, the multifunctional carbon nanotube (CNT) composites were prepared though the oxidation of dopamine at room temperature and subsequent electroless silver deposition by mildly stirring. The stable immobilization and direct electron transfer of glucose oxidase were achieved on the composite film modified glassy carbon electrode. The resulting electrode gave a well-defined redox peaks with a formal potential of about -482 mV (vs. SCE) in pH 7.0 buffer. The electron transfer rate constant was estimated to be 3.6 s(-1), due to the combined contribution of Pdop, CNTs and Ag nanoparticles with the help of Nafion. Furthermore, the method for detecting of glucose was proposed based on the decrease of oxygen caused by the enzyme-catalyzed reaction between glucose oxidase (GOD) and glucose. The linear response to glucose ranging from 50.0 μM to 1.1 mM (R(2)=0.9958), with a calculated detection limit of 17.0 μM at a signal-to-noise ratio of 3. The low calculated apparent Michaelis-Menten constant (K(M)(app)) was 5.46 mM, implying the high enzymatic activity and affinity of immobilized GOD for glucose. It can reasonably be expected that this observation might hold true for other noble metal nanostructure-electroactive protein systems, providing a promising platform for the development of biosensors and biofuel cells. Copyright © 2011 Elsevier B.V. All rights reserved.

  6. Direct electrochemistry of Phanerochaete chrysosporium cellobiose dehydrogenase covalently attached onto gold nanoparticle modified solid gold electrodes.

    PubMed

    Matsumura, Hirotoshi; Ortiz, Roberto; Ludwig, Roland; Igarashi, Kiyohiko; Samejima, Masahiro; Gorton, Lo

    2012-07-24

    Achieving efficient electrochemical communication between redox enzymes and various electrode materials is one of the main challenges in bioelectrochemistry and is of great importance for developing electronic applications. Cellobiose dehydrogenase (CDH) is an extracellular flavocytochrome composed of a catalytic FAD containing dehydrogenase domain (DH(CDH)), a heme b containing cytochrome domain (CYT(CDH)), and a flexible linker region connecting the two domains. Efficient direct electron transfer (DET) of CDH from the basidiomycete Phanerochaete chrysosporium (PcCDH) covalently attached to mixed self-assembled monolayer (SAM) modified gold nanoparticle (AuNP) electrode is presented. The thiols used were as follows: 4-aminothiophenol (4-ATP), 4-mercaptobenzoic acid (4-MBA), 4-mercaptophenol (4-MP), 11-mercapto-1-undecanamine (MUNH(2)), 11-mercapto-1-undecanoic acid (MUCOOH), and 11-mercapto-1-undecanol (MUOH). A covalent linkage between PcCDH and 4-ATP or MUNH(2) in the mixed SAMs was formed using glutaraldehyde as cross-linker. The covalent immobilization and the surface coverage of PcCDH were confirmed with surface plasmon resonance (SPR). To improve current density, AuNPs were cast on the top of polycrystalline gold electrodes. For all the immobilized PcCDH modified AuNPs electrodes, cyclic voltammetry exhibited clear electrochemical responses of the CYT(CDH) with fast electron transfer (ET) rates in the absence of substrate (lactose), and the formal potential was evaluated to be +162 mV vs NHE at pH 4.50. The standard ET rate constant (k(s)) was estimated for the first time for CDH and was found to be 52.1, 59.8, 112, and 154 s(-1) for 4-ATP/4-MBA, 4-ATP/4-MP, MUNH(2)/MUCOOH, and MUNH(2)/MUOH modified electrodes, respectively. At all the mixed SAM modified AuNP electrodes, PcCDH showed DET only via the CYT(CDH). No DET communication between the DH(CDH) domain and the electrode was found. The current density for lactose oxidation was remarkably increased by

  7. Direct electrochemistry of glucose oxidase immobilized on NdPO4 nanoparticles/chitosan composite film on glassy carbon electrodes and its biosensing application.

    PubMed

    Sheng, Qinglin; Luo, Kai; Li, Lei; Zheng, Jianbin

    2009-02-01

    The direct electrochemistry of glucose oxidase (GOx) immobilized on a composite matrix based on chitosan (CHIT) and NdPO(4) nanoparticles (NPs) underlying on glassy carbon electrode (GCE) was achieved. The cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the modified electrode. In deaerated buffer solutions, the cyclic voltammetry of the composite films of GOx/NdPO(4) NPs/CHIT showed a pair of well-behaved redox peaks that are assigned to the redox reaction of GOx, confirming the effective immobilization of GOx on the composite film. The electron transfer rate constant was estimated to be 5.0 s(-1). The linear dynamic range for the detection of glucose was 0.15-10 mM with a correlation coefficient of 0.999 and the detection limit was estimated at about 0.08 mM (S/N=3). The calculated apparent Michaelis-Menten constant was 2.5 mM, which suggested a high affinity of the enzyme-substrate. The immobilized GOx in the NdPO(4) NPs/CHIT composite film retained its bioactivity. Furthermore, the method presented here can be easily extended to immobilize and obtain the direct electrochemistry of other redox enzymes or proteins.

  8. 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.

  9. Protein Electrochemistry: Questions and Answers.

    PubMed

    Fourmond, V; Léger, C

    This chapter presents the fundamentals of electrochemistry in the context of protein electrochemistry. We discuss redox proteins and enzymes that are not photoactive. Of course, the principles described herein also apply to photobioelectrochemistry, as discussed in later chapters of this book. Depending on which experiment is considered, electron transfer between proteins and electrodes can be either direct or mediated, and achieved in a variety of configurations: with the protein and/or the mediator free to diffuse in solution, immobilized in a thick, hydrated film, or adsorbed as a sub-monolayer on the electrode. The experiments can be performed with the goal to study the protein or to use it. Here emphasis is on mechanistic studies, which are easier in the configuration where the protein is adsorbed and electron transfer is direct, but we also explain the interpretation of signals obtained when diffusion processes affect the response.This chapter is organized as a series of responses to questions. Questions 1-5 are related to the basics of electrochemistry: what does "potential" or "current" mean, what does an electrochemical set-up look like? Questions 6-9 are related to the distinction between adsorbed and diffusive redox species. The answers to questions 10-13 explain the interpretation of slow and fast scan voltammetry with redox proteins. Questions 14-19 deal with catalytic electrochemistry, when the protein studied is actually an enzyme. Questions 20, 21 and 22 are general.

  10. Electrochemistry in research and development

    SciTech Connect

    Kalvoda, R.; Parsons, R.

    1985-01-01

    This volume contains the typescript papers presented at the UNESCO Scientific Forum on Chemistry in the Service of Mankind, held in Paris in 1984. Areas covered include Electrochemistry and Energy, Electrochemistry and the Environment, Electrochemistry in Biosciences, and Electrochemistry in Technology.

  11. An aptamer-based biosensing platform for highly sensitive detection of platelet-derived growth factor via enzyme-mediated direct electrochemistry.

    PubMed

    Deng, Kun; Xiang, Yang; Zhang, Liqun; Chen, Qinghai; Fu, Weiling

    2013-01-08

    In this work, a new label-free electrochemical aptamer-based sensor (aptasensor) was constructed for detection of platelet-derived growth factor (PDGF) based on the direct electrochemistry of glucose oxidase (GOD). For this proposed aptasensor, poly(diallyldimethylammonium chloride) (PDDA)-protected graphene-gold nanoparticles (P-Gra-GNPs) composite was firstly coated on electrode surface to form the interface with biocompatibility and huge surface area for the adsorption of GOD layer. Subsequently, gold nanoclusters (GNCs) were deposited on the surface of GOD to capture PDGF binding aptamer (PBA). Finally, GOD as a blocking reagent was employed to block the remaining active sites of the GNCs and avoid the nonspecific adsorption. With the direct electron transfer of double layer GOD membranes, the aptasensor showed excellent electrochemical response and the peak current decreased linearly with increasing logarithm of PDGF concentration from 0.005 nM to 60 nM with a relatively low limit of detection of 1.7 pM. The proposed aptasensor exhibited high specificity, good reproducibility and long-term stability, which provided a new promising technique for aptamer-based protein detection. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Immobilization and direct electrochemistry of glucose oxidase on a tetragonal pyramid-shaped porous ZnO nanostructure for a glucose biosensor.

    PubMed

    Dai, Zhihui; Shao, Guojian; Hong, Jianmin; Bao, Jianchun; Shen, Jian

    2009-01-01

    A tetragonal pyramid-shaped porous ZnO (TPSP-ZnO) nanostructure is used for the immobilization, direct electrochemistry and biosensing of proteins. The prepared ZnO has a large surface area and good biocompatibility. Using glucose oxidase (GOD) as a model, this shaped ZnO is tested for immobilization of proteins and the construction of electrochemical biosensors with good electrochemical performances. The interaction between GOD and TPSP-ZnO is examined by using AFM, N(2) adsorption isotherms and electrochemical methods. The immobilized GOD at a TPSP-ZnO-modified glassy carbon electrode shows a good direct electrochemical behavior, which depends on the properties of the TPSP-ZnO. Based on a decrease of the electrocatalytic response of the reduced form of GOD to dissolved oxygen, the proposed biosensor exhibits a linear response to glucose concentrations ranging from 0.05 to 8.2mM with a detection limit of 0.01mM at an applied potential of -0.50V which has better biosensing properties than those from other morphological ZnO nanoparticles. The biosensor shows good stability, reproducibility, low interferences and can diagnose diabetes very fast and sensitively. Such the TPSP-ZnO nanostructure provides a good matrix for protein immobilization and biosensor preparation.

  13. Functionalization of carbon nanotubes with water-insoluble porphyrin in ionic liquid: direct electrochemistry and highly sensitive amperometric biosensing for trichloroacetic acid.

    PubMed

    Tu, Wenwen; Lei, Jianping; Ju, Huangxian

    2009-01-01

    A functional composite of single-walled carbon nanotubes (SWNTs) with hematin, a water-insoluble porphyrin, was first prepared in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) ionic liquid. The novel composite in ionic liquid was characterized by scanning electron microscopy, ultraviolet absorption spectroscopy, and electrochemical impedance spectroscopy, and showed a pair of direct redox peaks of the Fe(III)/Fe(II) couple. The composite-[BMIM][PF(6)]-modified glassy carbon electrode showed excellent electrocatalytic activity toward the reduction of trichloroacetic acid (TCA) in neutral media due to the synergic effect among SWNTs, [BMIM][PF(6)], and porphyrin, which led to a highly sensitive and stable amperometric biosensor for TCA with a linear range from 9.0x10(-7) to 1.4x10(-4) M. The detection limit was 3.8x10(-7) M at a signal-to-noise ratio of 3. The TCA biosensor had good analytical performance, such as rapid response, good reproducibility, and acceptable accuracy, and could be successfully used for the detection of residual TCA in polluted water. The functional composite in ionic liquid provides a facile way to not only obtain the direct electrochemistry of water-insoluble porphyrin, but also construct novel biosensors for monitoring analytes in real environmental samples.

  14. Direct electrochemistry and electrocatalysis of myoglobin based on silica-coated gold nanorods/room temperature ionic liquid/silica sol-gel composite film.

    PubMed

    Zhu, Wen-Lei; Zhou, Yang; Zhang, Jian-Rong

    2009-11-15

    A novel biosensor based on the silica-coated gold nanorods (GNRs@SiO(2)) and hydrophilic room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium tetrafluroborate ([bmim][BF(4)]) was fabricated for the determination of hydrogen peroxide (H(2)O(2)) and nitrite. GNRs@SiO(2) can not only act as a binder to hinder [bmim][BF(4)] (RTIL) leaking from the electrode surface, but also provide a favorable microenvironment for direct electrochemistry of myoglobin (Mb). A pair of well-defined and quasi-reversible redox peaks of Mb was obtained at the GNRs@SiO(2)-Mb/RTIL-sol-gel composite film modified GCE (GNRs@SiO(2)-Mb/RTIL-sol-gel/GCE) through direct electron transfer between Mb and the underlying electrode. This biosensor showed an excellent electrocatalytic activity towards hydrogen peroxide and nitrite. The linear range for the determination of H(2)O(2) was from 0.2 to 180 microM with a detection limit of 0.12 microM based on the signal-to-noise ratio of 3. In addition, the biosensor also exhibited high selectivity, good reproducibility, and long-term stability. Therefore, this kind of composite film can provide an ideal matrix for protein immobilization and biosensor fabrication.

  15. Al3+-directed self-assembly and their electrochemistry properties of three-dimensional dendriform horseradish peroxidase/polyacrylamide/platinum/single-walled carbon nanotube composite film.

    PubMed

    Xie, Jingsi; Feng, Xiumei; Hu, Jianqiang; Chen, Xiaohua; Li, Aiqing

    2010-01-15

    A novel general methodology for protein immobilization and third-generation biosensor construction is demonstrated, which involves Al(3+)-directed polyacrylamide (PAM) self-assembly into an ordered dendriform structure, easily immobilizing enzymes and nanoparticles. Platinum/single-walled carbon nanotube (Pt/SWCNT) heterojunction nanomaterials were for the first time fabricated via an EDTA-directed synthesis strategy. The Pt/SWCNTs were employed as a supporting matrix to explore a novel immobilization and biosensing platform of redox proteins through cooperating Al(3+)-directed PAM self-assembly. Compared with the almost single-layer horseradish peroxidase (HRP)/PAM film electrode, multilayer HRP/PAM/Pt/SWCNT film electrode exhibited a pair of much stronger redox peaks at -0.22 V (vs. Ag/AgCl). Moreover, with advantages of the ordered multilayer HRP/PAM/Pt/SWCNT film, facilitated direct electron transfer of the metalloenzymes with an apparent heterogeneous electron transfer rate constant (k(s)) of 14.94+/-1.36 s(-1) and smaller peak-to-peak separation (DeltaE(p)) of about 37 mV was acquired on the PAM/Pt/SWCNT-based enzyme electrode. The PAM/Pt/SWCNT-based biosensor demonstrated significant electrocatalytic activity for the reduction of hydrogen peroxide with a small apparent Michaelis-Menten constant (87 microM), wide linear range (1-270 microM), very low detection limit (0.08 microM, S/N=3), and high sensitivity (372 mA cm(-2) M(-1)). Together, these indicated that the Al(3+)-directed HRP/PAM/Pt/SWCNT film was one of ideal candidate materials for direct electrochemistry of redox proteins and the construction of the related enzyme biosensors, and may find potential applications in biomedical, food, and environmental analysis and detection. Copyright 2009 Elsevier B.V. All rights reserved.

  16. Direct modeling of the electrochemistry in the three-phase boundary of solid oxide fuel cell anodes by density functional theory: a critical overview.

    PubMed

    Shishkin, M; Ziegler, T

    2014-02-07

    The first principles modeling of electrochemical reactions has proven useful for the development of efficient, durable and low cost solid oxide full cells (SOFCs). In this account we focus on recent advances in modeling of structural, electronic and catalytic properties of the SOFC anodes based on density functional theory (DFT) first principle calculations. As a starting point, we highlight that the adequate analysis of cell electrochemistry generally requires modeling of chemical reactions at the metal/oxide interface rather than on individual metal or oxide surfaces. The atomic models of Ni/YSZ and Ni/CeO2 interfaces, required for DFT simulations of reactions on SOFC anodes are discussed next, together with the analysis of the electronic structure of these interfaces. Then we proceed to DFT-based findings on charge transfer mechanisms during redox reactions on these two anodes. We provide a comparison of the electronic properties of Ni/YSZ and Ni/CeO2 interfaces and present an interpretation of their different chemical performances. Subsequently we discuss the computed energy pathways of fuel oxidation mechanisms, obtained by various groups to date. We also discuss the results of DFT studies combined with microkinetic modeling as well as the results of kinetic Monte Carlo simulations. In conclusion we summarize the key findings of DFT modeling of metal/oxide interfaces to date and highlight possible directions in the future modeling of SOFC anodes.

  17. Nanocrystalline TiO2 films containing sulfur and gold: Synthesis, characterization and application to immobilize and direct electrochemistry of cytochrome c

    NASA Astrophysics Data System (ADS)

    Rafiee-Pour, Hossain-Ali; Hamadanian, Masood; Koushali, Samaneh Katebi

    2016-02-01

    In this paper, nanoporous titanium dioxide (TiO2) film was used for cytochrome c (cyt c) immobilization as an electrode substrate for electrochemical redox activity of the adsorbed cyt c. The result of cyclic voltammetry exhibited a pair of well-defined and quasi-reversible peaks for direct electron transfer of cyt c (formal potential [E0‧ = (Epa + Epc)/2] of 53 mV versus Ag/AgCl). In addition the effect of metal and nonmetal ions (Au, S) co-doping on the efficiency of TiO2 nanoparticles (prepared by combining sol-gel and photo-deposition methods) on the cyt c immobilization process was investigated. The results exhibited that the Au, S-co-doped TiO2 (Au/S-TiO2) with a spheroidal shape demonstrates a smaller grain size than the pure TiO2. Meanwhile, the UV-vis DRS of Au/S-TiO2 showed a considerable red shift to the visible region. As a result, it was found that 4% Au/0.1% S-TiO2 had the highest efficiency for cytochrome c immobilization. The results showed that the peak currents were higher after the annealing of the TiO2 film. This observation suggests that the use of TiO2 films may be advantageous for the development of nanoporous biosensors employing reductive electrochemistry.

  18. Effect of the structure of imidazolium cations in [BF4](-)-type ionic liquids on direct electrochemistry and electrocatalysis of horseradish peroxidase in Nafion films.

    PubMed

    Lu, Lu; Huang, Xirong; Qu, Yinbo

    2011-10-01

    The direct electrochemistry and bioelectrocatalysis of horseradish peroxidase (HRP) in Nafion films at glassy carbon electrode (GCE) was investigated in three [BF(4)](-)-type room-temperature ionic liquids (ILs) to understand the structural effect of imidazolium cations. The three ILs are 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim][BF(4)]), 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) and 1-hexyl-3-methylimidazolium tetrafluoroborate ([Hmim][BF(4)]). A small amount of water in the three ILs is indispensable for maintaining the electrochemical activity of HRP in Nafion films, and the optimum water contents decrease with the increase of alkyl chain length on imidazole ring. Analysis shows that the optimum water contents are primarily determined by the hydrophilicity of ILs used. In contrast to aqueous medium, ILs media facilitate the direct electron transfer of HRP, and the electrochemical parameters obtained in different ILs are obviously related to the nature of ILs. The direct electron transfer between HRP and GCE is a surface-confined quasi-reversible single electron transfer process. The apparent heterogeneous electron transfer rate constant decreases gradually with the increase of alkyl chain length on imidazole ring, but the changing extent is relatively small. The electrocatalytic reduction current of H(2)O(2) at the present electrode decreases obviously with the increase of alkyl chain length, and the mass transfer of H(2)O(2) via diffusion in ILs should be responsible for the change. In addition, the modified electrode has good stability and reproducibility; the ability to tolerate high levels of F(-) has been greatly enhanced due to the use of Nafion film. When an appropriate mediator is included in the sensing layer, a sensitive nonaqueous biosensor could be fabricated. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Direct electrochemistry and electrocatalytic properties of hemoglobin immobilized on a carbon ionic liquid electrode modified with mesoporous molecular sieve MCM-41.

    PubMed

    Li, Yonghong; Zeng, Xiandong; Liu, Xiaoying; Liu, Xinsheng; Wei, Wanzhi; Luo, Shenglian

    2010-08-01

    The direct electron transfer and electrocatalysis of hemoglobin (Hb) entrapped in the MCM-41 modified carbon ionic liquid electrode (CILE) were investigated by using cyclic voltammetry in 0.10 M pH 7.0 phosphate buffer solution (PBS). Due to its uniform pore structure, high surface areas and good biocompatibility, the mesoporous silica sieve MCM-41 provided a suitable matrix for immobilization of biomolecule. The MCM-41 modified CILE showed significant promotion to the direct electron transfer of Hb, which exhibited a pair of well defined and quasi-reversible peaks for heme Fe(III)/Fe(II) with a formal potential of -0.284 V (vs. Ag/AgCl). Additionally, the Hb immobilized on the MCM-41 modified carbon ionic liquid electrode showed excellent electrocatalytic activity toward H(2)O(2). The electrocatalytic current values were linear with increasing concentration of H(2)O(2) in a wide range of 5-310 microM and the corresponding detection limit was calculated to be 5 x 10(-8)M (S/N=3). The surface coverage of Hb immobilized on the MCM-41 modified carbon ionic liquid electrode was about 2.54 x 10(-9) molcm(-2). The Michaelis-Menten constant K(m)(app) of 214 microM indicated that the Hb immobilized on the modified electrode showed high affinity to H(2)O(2). The proposed electrode had high stability and good reproducibility due to the protection effect of MCM-41 and ionic liquid, and it would have wide potential applications in direct electrochemistry, biosensors and biocatalysis.

  20. Folds and Etudes

    ERIC Educational Resources Information Center

    Bean, Robert

    2007-01-01

    In this article, the author talks about "Folds" and "Etudes" which are images derived from anonymous typing exercises that he found in a used copy of "Touch Typing Made Simple". "Etudes" refers to the musical tradition of studies for a solo instrument, which is a typewriter. Typing exercises are repetitive attempts to type words and phrases…

  1. Direct electrochemistry and electrocatalysis of heme proteins immobilised in carbon-coated nickel magnetic nanoparticle-chitosan-dimethylformamide composite films in room-temperature ionic liquids.

    PubMed

    Wang, Ting; Wang, Lu; Tu, Jiaojiao; Xiong, Huayu; Wang, Shengfu

    2013-12-01

    The direct electrochemistry and electrocatalysis of heme proteins entrapped in carbon-coated nickel magnetic nanoparticle-chitosan-dimethylformamide (CNN-CS-DMF) composite films were investigated in the hydrophilic ionic liquid [bmim][BF4]. The surface morphologies of a representative set of films were characterised via scanning electron microscopy. The proteins immobilised in the composite films were shown to retain their native secondary structure using UV-vis spectroscopy. The electrochemical performance of the heme proteins-CNN-CS-DMF films was evaluated via cyclic voltammetry and chronoamperometry. A pair of stable and well-defined redox peaks was observed for the heme protein films at formal potentials of -0.151 V (HRP), -0.167 V (Hb), -0.155 V (Mb) and -0.193 V (Cyt c) in [bmim][BF4]. Moreover, several electrochemical parameters of the heme proteins were calculated by nonlinear regression analysis of the square-wave voltammetry. The addition of CNN significantly enhanced not only the electron transfer of the heme proteins but also their electrocatalytic activity toward the reduction of H2O2. Low apparent Michaelis-Menten constants were obtained for the heme protein-CNN-CS-DMF films, demonstrating that the biosensors have a high affinity for H2O2. In addition, the resulting electrodes displayed a low detection limit and improved sensitivity for detecting H2O2, which indicates that the biocomposite film can serve as a platform for constructing new non-aqueous biosensors for real detection. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Direct electrochemistry of catalase at multiwalled carbon nanotubes-nafion in presence of needle shaped DDAB for H2O2 sensor.

    PubMed

    Arun Prakash, Periasamy; Yogeswaran, Umasankar; Chen, Shen-Ming

    2009-06-15

    The direct electrochemistry of catalase (CAT) at didodecyldimethylammonium bromide (DDAB) present on nafion dispersed multiwalled carbon nanotubes (MWCNTs-NF) modified glassy carbon electrode (GCE) has been reported. The presence of DDAB in MWCNTs-NF-CAT film enhances the surface coverage concentration of CAT (Fe(III/II)) to 48%. Similarly, in presence of DDAB, there is a 57% enhancement in electron transfer rate (ks) with 66% increase in CAT stability. (Fe(III/II)) redox couple exhibits linear dependence with the pH variation (-51 mV pH(-1)). The UV-vis absorption spectroscopy study reveals the entrapped CAT in DDAB film retains its native structure at MWCNTs-NF modified electrodes. Similarly, electrochemical impedance spectroscopy results confirm the co-existence of CAT and DDAB in the modified film. Further, scanning electron microscopy results reveal the structural morphological difference between various components in MWCNTs-NF-(DDAB/CAT) film. The cyclic voltammetry (CV) and amperometry (i-t curve) have been used for the measurement of electroanalytical properties of H2O2 by means of various film modified GCEs. The sensitivity values of MWCNTs-NF-(DDAB/CAT) film for H2O2 using CV (35.62 microA mM(-1)cm2) are higher than the values which are obtained for MWCNTs-NF-CAT film (2.74 mmicroA mM(-1)cm2). Similarly, the sensitivity values using i-t curve are 101.74 microA mM(-1)cm2 for MWCNTs-NF-(DDAB/CAT) and 74.69 microA mM(-1)cm2 for MWCNTs-NF-CAT film. Finally, the diffusion coefficient of H2O2 at MWCNTs-NF-(DDAB/CAT) film (3.4 x 10(-10) cm2 s(-1)) has been calculated using rotating disc electrode studies.

  3. Binding and Direct Electrochemistry of OmcA, an Outer-Membrane Cytochrome from an Iron Reducing Bacterium, with Oxide Electrodes: A Candidate Biofuel Cell System

    SciTech Connect

    Eggleston, Carrick M.; Voros, Janos; Shi, Liang; Lower, Brian H.; Droubay, Timothy C.; Colberg, Patricia J.

    2008-02-15

    Dissimilatory iron-reducing bacteria transfer electrons to solid ferric respiratory electron acceptors. Outer-membrane cytochromes expressed by these organisms are of interest in both microbial fuel cells and biofuel cells. We use optical waveguide lightmode spectroscopy (OWLS) to show that OmcA, an 85 kDa decaheme outer-membrane c-type cytochrome from Shewanella oneidensis MR-1, adsorbs to isostructural Al2O3 and Fe2O3 in similar amounts. Adsorption is ionic-strength and pH dependent (peak adsorption at pH 6.5–7.0). The thickness of the OmcA layer on Al2O3 at pH 7.0 [5.8 ± 1.1 (2r) nm] from OWLS is similar, within error, to that observed using atomic force microscopy (4.8 ± 2 nm). The highest adsorption density observed was 334 ng cm 2 (2.4 · 1012 molecules cm 2), corresponding to a monolayer or 9.9 nm diameter spheres or submonolayer coverage by smaller molecules. Direct electrochemistry of OmcA on Fe2O3 electrodes was observed using cyclic voltammetry, with cathodic peak potentials of 380 to 320 mV versus Ag/AgCl. Variations in the cathodic peak positions are speculatively attributed to redox-linked conformation change or changes in molecular orientation. OmcA can exchange electrons with ITO electrodes at higher current densities than with Fe2O3. Overall, OmcA can bind to and exchange electrons with several oxides, and thus its utility in fuel cells is not restricted to Fe2O3.

  4. Imidazoline derivative templated synthesis of broccoli-like Bi2S3 and its electrocatalysis towards the direct electrochemistry of hemoglobin.

    PubMed

    Chen, Xiaoqian; Wang, Qingxiang; Wang, Liheng; Gao, Feng; Wang, Wei; Hu, Zhengshui

    2015-04-15

    A broccoli-like bismuth sulfide (bBi2S3) was synthesized via a solvothermal method using a self-made imidazoline derivative of 2-undecyl-1-dithioureido-ethyl-imidazoline as the soft template. The morphology and chemical constitution of the product were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). Electrochemical characterization experiments show that the bBi2S3 has the higher specific surface area and standard heterogeneous electron transfer rate constant than the rod-like Bi2S3 (rBi2S3). Hemoglobin (Hb) was then chosen as a protein model to investigate the electrocatalytic property of the synthesized bBi2S3. The results show that Hb entrapped in the composite film of chitosan and bBi2S3 displays an excellent direct electrochemistry, and retains its biocatalytic activity toward the electro-reduction of hydrogen peroxide. The current response in the amperometry shows a linear response to H2O2 concentrations in the range from 0.4 to 4.8µM with high sensitivity (444µAmM(-1)) and low detection limit (0.096µM). The Michaelis-Menten constant (KM(app)) of the fabricated bioelectrode for H2O2 was determined as low as 1µM. These results demonstrate that the synthesized bBi2S3 offers a new path for the immobilization of redox-active protein and the construction of the third-generation biosensors.

  5. Preparation and electrochemistry of Pd-Ni/Si nanowire nanocomposite catalytic anode for direct ethanol fuel cell.

    PubMed

    Miao, Fengjuan; Tao, Bairui; Chu, Paul K

    2012-04-28

    A new silicon-based anode suitable for direct ethanol fuel cells (DEFCs) is described. Pd-Ni nanoparticles are coated on Si nanowires (SiNWs) by electroless co-plating to form the catalytic materials. The electrocatalytic properties of the SiNWs and ethanol oxidation on the Pd-Ni catalyst (Pd-Ni/SiNWs) are investigated electrochemically. The effects of temperature and working potential limit in the anodic direction on ethanol oxidation are studied by cyclic voltammetry. The Pd-Ni/SiNWs electrode exhibits higher electrocatalytic activity and better long-term stability in an alkaline solution. It also yields a larger current density and negative onset potential thus boding well for its application to fuel cells.

  6. Investigating the thermostability of succinate: quinone oxidoreductase enzymes by direct electrochemistry at SWNTs-modified electrodes and FTIR spectroscopy

    PubMed Central

    Melin, Frederic; Noor, Mohamed R.; Pardieu, Elodie; Boulmedais, Fouzia; Banhart, Florian; Cecchini, Gary; Soulimane, Tewfik

    2015-01-01

    Succinate Quinone reductases (SQRs) are the enzymes which couple the oxidation of succinate and the reduction of quinones in the respiratory chain of prokaryotes and eukaryotes. We compare herein the temperature-dependent activity and structural stability of two SQRs, the first one from the mesophilic bacterium E. coli and the second one from the thermophilic bacterium T. thermophilus by a combined electrochemical and infrared spectroscopy approach. Direct electron transfer was achieved with the full membrane protein complexes at SWNTs-modified electrodes. The possible structural factors which contribute to the temperature-dependent activity of the enzymes and to the thermostability of the T. thermophiles SQR in particular, are discussed. PMID:25139263

  7. 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.

  8. A glucose biosensor based on direct electrochemistry of glucose oxidase immobilized onto platinum nanoparticles modified graphene electrode

    NASA Astrophysics Data System (ADS)

    Liu, AiRong; Huang, ShiMing

    2012-07-01

    The platinum nanoparticles were adsorbed on graphene oxide sheets and played an important role in catalytic reduction of graphene oxide with hydrazine, leading to the formation of graphene-Pt nanoparticles. Because of their good electronic properties, biocompatibility and high surface area, graphene-Pt based composites achieved the direct electron transfer of redox enzyme and maintained their bioactivity well. The graphene-Pt nanocomposites were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED). The amperometric biosensor fabricated by depositing glucose oxidase over Nafion-solubilized graphene-Pt electrode retained its biocatalytic activity and has offered fast and sensitive glucose quantification.

  9. An electrochemical aptasensor for thrombin detection based on direct electrochemistry of glucose oxidase using a functionalized graphene hybrid for amplification.

    PubMed

    Bai, Lijuan; Yan, Bin; Chai, Yaqin; Yuan, Ruo; Yuan, Yali; Xie, Shunbi; Jiang, Liping; He, Ying

    2013-11-07

    In this work, we reported a new label-free electrochemical aptasensor for highly sensitive detection of thrombin using direct electron transfer of glucose oxidase (GOD) as a redox probe and a gold nanoparticle-polyaniline-graphene (Au-PANI-Gra) hybrid for amplification. The Au-PANI-Gra hybrid with large surface area provided a biocompatible sensing platform for the immobilization of GOD. GOD was encapsulated into the three-dimensional netlike (3-mercaptopropyl)trimethoxysilane (MPTS) to form the MPTS-GOD biocomposite, which not only retained the native functions and properties, but also exhibited tunable porosity, high thermal stability, and chemical inertness. With abundant thiol tail groups on MPTS, MPTS-GOD was able to chemisorb onto the surface of the Au-PANI-Gra modified electrode through the strong affinity of the Au-S bond. The electrochemical signal originated from GOD, avoiding the addition or labeling of other redox mediators. After immobilizing the thiolated thrombin binding aptamer through gold nanoparticles (AuNPs), GOD as a blocking reagent was employed to block the remaining active sites of the AuNPs and avoid the nonspecific adsorption. The proposed method avoided the labeling process of redox probes and increased the amount of electroactive GOD. The concentration of thrombin was monitored based on the decrease of current response through cyclic voltammetry (CV) in 0.1 M PBS (pH 7.4). With the excellent direct electron transfer of double layer GOD membranes, the resulting aptasensor exhibited high sensitivity for detection of thrombin with a wide linear range from 1.0 × 10(-12) to 3.0 × 10(-8) M. The proposed aptasensor also showed good stability, satisfactory reproducibility and high specificity, which provided a promising strategy for electrochemical aptamer-based detection of other biomolecules.

  10. Direct electrochemistry of glucose oxidase and biosensing for glucose based on carbon nanotubes@SnO(2)-Au composite.

    PubMed

    Li, Fenghua; Song, Jixia; Li, Fei; Wang, Xiaodan; Zhang, Qixian; Han, Dongxue; Ivaska, Ari; Niu, Li

    2009-12-15

    Multiwalled carbon nanotubes@SnO(2)-Au (MWCNTs@SnO(2)-Au) composite was synthesized by a chemical route. The structure and composition of the MWCNTs@SnO(2)-Au composite were confirmed by means of transmission electron microscopy, X-ray photoelectron and Raman spectroscopy. Due to the good electrocatalytic property of MWCNTs@SnO(2)-Au composite, a glucose biosensor was constructed by absorbing glucose oxidase (GOD) on the hybrid material. A direct electron transfer process is observed at the MWCNTs@SnO(2)-Au/GOD-modified glassy carbon electrode. The glucose biosensor has a linear range from 4.0 to 24.0mM, which is suitable for glucose determination by real samples. It should be worthwhile noting that, from 4.0 to 12.0mM, the cathodic peak currents of the biosensor decrease linearly with increasing the glucose concentrations in human blood. Meanwhile, the resulting biosensor can also prevent the effects of interfering species. Moreover, the biosensor exhibits satisfying reproducibility, good operational stability and storage stability. Therefore, the MWCNTs@SnO(2)-Au/GOD biocomposite could be promisingly applied to determine blood sugar concentration in the practical clinical analysis.

  11. Hierarchically structured one-dimensional TiO2 for protein immobilization, direct electrochemistry, and mediator-free glucose sensing.

    PubMed

    Si, Peng; Ding, Shujiang; Yuan, Jun; Lou, Xiong Wen David; Kim, Dong-Hwan

    2011-09-27

    A novel one-dimensional hierarchically structured TiO(2) (1DHS TiO(2)) was synthesized by a solvothermal method using multiwalled carbon nanotubes (MWCNTs) as a template and evaluated for the immobilization of protein and biosensing applications. Characterization studies showed that the 1DHS TiO(2) possessed an anatase crystalline structure and a large surface area with narrow pore size distribution. Fast direct electron transfer was observed for glucose oxidase (GOx) immobilized on the 1DHS TiO(2), and excellent electrocatalytic performance for glucose detection can be obtained without a mediator. The glucose sensor based on the GOx/1DHS TiO(2)-modified electrode had a high sensitivity of 9.90 μA mM(-1) cm(-2) and a low detection limit of 1.29 μM. The fabricated biosensor displayed good selectivity and long-term stability, indicating that the novel structured TiO(2) is a promising material for the immobilization of biomolecules and the fabrication of third-generation biosensors. © 2011 American Chemical Society

  12. Reduced graphene oxide/PAMAM-silver nanoparticles nanocomposite modified electrode for direct electrochemistry of glucose oxidase and glucose sensing.

    PubMed

    Luo, Zhimin; Yuwen, Lihui; Han, Yujie; Tian, Jing; Zhu, Xingrong; Weng, Lixing; Wang, Lianhui

    2012-01-01

    Reduced graphene oxide/PAMAM-silver nanoparticles nanocomposite (RGO-PAMAM-Ag) was synthesized by self-assembly of carboxyl-terminated PAMAM dendrimer (PAMAM-G3.5) on graphene oxide (GO) as growing template, and in-situ reduction of both AgNO(3) and GO under microwave irradiation. The RGO-PAMAM-Ag nanocomposite was used as a novel immobilization matrix for glucose oxidase (GOD) and exhibited excellent direct electron transfer properties for GOD with the rate constant (K(s)) of 8.59 s(-1). The fabricated glucose biosensor based on GOD electrode modified with RGO-PAMAM-Ag nanocomposite displayed satisfactory analytical performance including high sensitivity (75.72 μA mM(-1) cm(-2)), low detection limit (4.5 μM), an acceptable linear range from 0.032 mM to 1.89 mM, and also preventing the interference of some interfering species usually coexisting with glucose in human blood at the work potential of -0.25 V. These results indicated that RGO-PAMAM-Ag nanocomposite is a promising candidate material for high-performance glucose biosensors.

  13. Direct electrochemistry and reagentless biosensing of glucose oxidase immobilized on chitosan wrapped single-walled carbon nanotubes.

    PubMed

    Zhou, Yi; Yang, Hui; Chen, Hong-Yuan

    2008-07-15

    Single-walled carbon nanotubes (SWCNTs) selectively wrapped by a water-soluble, environmentally friendly, biocompatible polymer chitosan (CHI) were employed for the construction of a bioelectrochemical platform for the direct electron transfer (DET) of glucose oxidase (GOD) and biosensing purposes. Scanning electron microscopy and Raman spectroscopy were used to investigate the properties of the SWCNT-CHI film. The results show that the preferentially wrapped small-diameter SWCNTs are dispersed within the CHI film and exist on the surface of the electrode as small bundles. The DET between GOD and the electrode surface was observed with a formal potential of about ca. -460 mV vs. SCE in phosphate buffer solution. The heterogeneous electron transfer rate constant and the surface coverage of GOD are estimated to be 3.0 s(-1) and 1.3 x 10(-10)mol/cm(2), respectively. The experimental results demonstrate that the immobilized GOD retains its catalytic activity towards the oxidation of glucose. Such a GOD/SWCNT-CHI film-based biosensor not only exhibits a rapid response time, a wide linear rang and a low detection limits at a detection potential of -400 mV but also shows the effective anti-interference capability. Significantly improved analytical capabilities of the GOD/SWCNT-CHI/GC electrode could be ascribed to the unique properties of the individual SWCNTs and to the biocompatibility of CHI.

  14. PEI-coated gold nanoparticles decorated with laccase: a new platform for direct electrochemistry of enzymes and biosensing applications.

    PubMed

    Brondani, Daniela; de Souza, Bernardo; S Souza, Bruno; Neves, Ademir; C Vieira, Iolanda

    2013-04-15

    This paper describes the synthesis and characterization of PEI-coated gold nanoparticles (PEI-AuNP), which were applied as a new platform in the immobilization of laccase (LAC) originating from Aspergillus oryzae. This material (PEI-AuNP-LAC) was used in the construction of a biosensor based on a glassy carbon electrode coated with a bio-nanostructured film. The occurrence of direct electron transfer (DET) between the electroactive center of LAC and the electrode surface was observed by cyclic voltammetry (CV), suggesting that the presence of AuNP in the film acts as a bridge for electron transfer. In acetate buffer solution (pH 5.0), LAC shows a pair of well-defined redox waves with a formal potential (E⁰') of 0.226V vs. Ag/AgCl (3M KCl). The biosensor response indicated a surface-controlled process with an apparent electron transfer rate constant (k(s)) of 0.4 s⁻¹, charge transfer coefficient (α) of 0.5, and surface coverage concentration (Γ) of 3.45×10⁻¹⁰ mol cm⁻². The optimized biosensor showed the following limits of detection (LOD) for the phenolic compounds tested: 0.03 μM for catechol and guaiacol; 0.14 μM for pyrogallol and 0.21 μM for hydroquinone, using square-wave voltammetry (SWV). The proposed biosensor demonstrated high sensitivity, good repeatability and reproducibility, and long-term stability (only 20% decrease in response over 90 days and after 150 measurements by SWV for each film formed). This biosensor was successfully applied to catechol quantification in spiked water samples. Furthermore, this method showed great potential for application in the development of new devices for biosensing. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Syntheses of fully sulfonated polyaniline nano-networks and its application to the direct electrochemistry of cytochrome c.

    PubMed

    Zhang, Lei; Jiang, Xiue; Niu, Li; Dong, Shaojun

    2006-01-15

    Fully sulfonated polyaniline nano-particles, nano-fibrils and nano-networks have been achieved for the first time by electrochemical homopolymerization of orthanilic acid using a three-step electrochemical deposition procedure in a mixed solvent of acetonitrile (ACN) and water. The diameter of the uniform nano-particles is about 60 nm, and the nano-fibrils can be organized in two-dimensional (2D) or three-dimensional (3D) non-periodic networks with good electrical contact. Average distance between contacts is about 850 and 600nm for a 2D and 3D system, respectively. The details of the poly(orthanilic acid) (POA) nano-structure were examined with a field emission scanning electron microscope (SEM). The structure and properties of POA were characterized with FTIR, UV-vis and electrochemical methods. The 3D POA nano-networks coated platinum electrode gave a direct electrochemical behavior of horse heart cytochrome c (Cyt c) immobilized on this electrode surface, a pair of well-defined redox waves with formal potential (E( degrees ')) of -0.032 V (versus Ag/AgCl) was achieved. The interaction between Cyt c and POA makes the formal potential shift negatively compared to that of Cyt c in solution. Spectrophotometric and electrochemical methods were used to investigate the interaction of Cyt c with POA. The immobilized Cyt c in the nano-networks POA film maintained its activity, showing a surface-controlled electrode process with the electron transfer rate constant (k(s)) of 21s(-1) and a of 0.53, and could be used for the electrocatalytic reduction of hydrogen peroxide. The quantitative determination of Cyt c by differential pulse voltammetry (DPV) using the fully sulfonated 3D POA nano-networks film coated platinum electrode was also studied.

  16. Direct electrochemistry and bioelectrocatalysis of a class II non-symbiotic plant haemoglobin immobilised on screen-printed carbon electrodes.

    PubMed

    Chekin, Fereshteh; Leiva, Nélida; Raoof, Jahan Bakhsh; Gorton, Lo; Bülow, Leif

    2010-10-01

    In this study, direct electron transfer (ET) has been achieved between an immobilised non-symbiotic plant haemoglobin class II from Beta vulgaris (nsBvHb2) and three different screen-printed carbon electrodes based on graphite (SPCE), multi-walled carbon nanotubes (MWCNT-SPCE), and single-walled carbon nanotubes (SWCNT-SPCE) without the aid of any electron mediator. The nsBvHb2 modified electrodes were studied with cyclic voltammetry (CV) and also when placed in a wall-jet flow through cell for their electrocatalytic properties for reduction of H(2)O(2). The immobilised nsBvHb2 displayed a couple of stable and well-defined redox peaks with a formal potential (E°') of -33.5 mV (vs. Ag|AgCl|3 M KCl) at pH 7.4. The ET rate constant of nsBvHb2, k(s), was also determined at the surface of the three types of electrodes in phosphate buffer solution pH 7.4, and was found to be 0.50 s(-1) on SPCE, 2.78 s(-1) on MWCNT-SPCE and 4.06 s(-1) on SWCNT-SPCE, respectively. The average surface coverage of electrochemically active nsBvHb2 immobilised on the SPCEs, MWCNT-SPCEs and SWCNT-SPCEs obtained was 2.85 × 10(-10) mol cm(-2), 4.13 × 10(-10) mol cm(-2) and 5.20 × 10(-10) mol cm(-2). During the experiments the immobilised nsBvHb2 was stable and kept its electrochemical and catalytic activities. The nsBvHb2 modified electrodes also displayed an excellent response to the reduction of hydrogen peroxide (H(2)O(2)) with a linear detection range from 1 μM to 1000 μM on the surface of SPCEs, from 0.5 μM to 1000 μM on MWCNT-SPCEs, and from 0.1 μM to 1000 μM on SWCNT-SPCEs. The lower limit of detection was 0.8 μM, 0.4 μM and 0.1 μM at 3σ at the SPCEs, the MWCNT-SPCEs, and the SWCNT-SPCEs, respectively, and the apparent Michaelis-Menten constant, K(M)(app), for the H(2)O(2) sensors was estimated to be 0.32 mM , 0.29 mM and 0.27 mM, respectively.

  17. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.

    1992-05-01

    This project seeks to advance the fundamental understanding of the physicochemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. A novel approach to the study of pyrite aqueous electrochemistry is proposed, based on the use of both synthetic and natural (i.e. coal-derived) pyrite specimens, the utilization of pyrite both in the form of micro (i.e. colloidal and subcolloidal) and macro (i.e. rotating ring disk)-electrodes, and the application of in-situ direct electroanalytical and spectroelectrochemical characterization techniques. Central to this research is the recognition that pyrite is a semiconductor material. (Photo)electrochemical experiments will be conducted to unravel the mechanisms of anodic and cathodic processes such as those associated with pyrite decomposition and the reduction of oxidants such as molecular oxygen and the ferric ion.

  18. DNA-Mediated Electrochemistry

    PubMed Central

    Gorodetsky, Alon A.; Buzzeo, Marisa C.

    2009-01-01

    The base pair stack of DNA has been demonstrated as a medium for long range charge transport chemistry both in solution and at DNA-modified surfaces. This chemistry is exquisitely sensitive to structural perturbations in the base pair stack as occur with lesions, single base mismatches, and protein binding. We have exploited this sensitivity for the development of reliable electrochemical assays based on DNA charge transport at self-assembled DNA monolayers. Here we discuss the characteristic features, applications, and advantages of DNA-mediated electrochemistry. PMID:18980370

  19. Electrochemistry and Storage

    NASA Technical Reports Server (NTRS)

    Thaller, L. H.

    1984-01-01

    The term electrochemistry implies the use of devices that convert chemical energy into electrical energy and sometimes vice versa. These devices are usually composed of some number of individual cells that are connected together to form a battery. In the cases where these devices cannot be electrically recharged they are usually referred to as primary batteries, whereas if these batteries can be charged and recharged repeatedly, they are called secondary batteries. The past and present uses of primary and secondary batteries in aerospace applications are discussed.

  20. Electrochemistry in supercritical fluids

    PubMed Central

    Branch, Jack A.; Bartlett, Philip N.

    2015-01-01

    A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide–acetonitrile and supercritical HFCs. PMID:26574527

  1. Electrochemistry in supercritical fluids.

    PubMed

    Branch, Jack A; Bartlett, Philip N

    2015-12-28

    A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide-acetonitrile and supercritical HFCs.

  2. Dynamic Electrochemistry: Methodology and Applications.

    ERIC Educational Resources Information Center

    Johnson, Dennis C.; And Others

    1984-01-01

    Reviews literature dealing with novel developments or important trends in electrochemistry. Areas examined include mass transfer, electrode kinetics, surface effects, chemically modified electrodes, coulostatic/galvanostatic methods, bioelectrochemistry, spectroelectrochemistry, and electrode instrumentation. Books, textbooks, and literature…

  3. Dynamic Electrochemistry: Methodology and Applications.

    ERIC Educational Resources Information Center

    Johnson, Dennis C.; And Others

    1984-01-01

    Reviews literature dealing with novel developments or important trends in electrochemistry. Areas examined include mass transfer, electrode kinetics, surface effects, chemically modified electrodes, coulostatic/galvanostatic methods, bioelectrochemistry, spectroelectrochemistry, and electrode instrumentation. Books, textbooks, and literature…

  4. Students' understandings of electrochemistry

    NASA Astrophysics Data System (ADS)

    O'Grady-Morris, Kathryn

    Electrochemistry is considered by students to be a difficult topic in chemistry. This research was a mixed methods study guided by the research question: At the end of a unit of study, what are students' understandings of electrochemistry? The framework of analysis used for the qualitative and quantitative data collected in this study was comprised of three categories: types of knowledge used in problem solving, levels of representation of knowledge in chemistry (macroscopic, symbolic, and particulate), and alternative conceptions. Although individually each of the three categories has been reported in previous studies, the contribution of this study is the inter-relationships among them. Semi-structured, task-based interviews were conducted while students were setting up and operating electrochemical cells in the laboratory, and a two-tiered, multiple-choice diagnostic instrument was designed to identify alternative conceptions that students held at the end of the unit. For familiar problems, those involving routine voltaic cells, students used a working-forwards problem-solving strategy, two or three levels of representation of knowledge during explanations, scored higher on both procedural and conceptual knowledge questions in the diagnostic instrument, and held fewer alternative conceptions related to the operation of these cells. For less familiar problems, those involving non-routine voltaic cells and electrolytic cells, students approached problem-solving with procedural knowledge, used only one level of representation of knowledge when explaining the operation of these cells, scored higher on procedural knowledge than conceptual knowledge questions in the diagnostic instrument, and held a greater number of alternative conceptions. Decision routines that involved memorized formulas and procedures were used to solve both quantitative and qualitative problems and the main source of alternative conceptions in this study was the overgeneralization of theory

  5. Transformations of the FeS Clusters of the Methylthiotransferases MiaB and RimO, Detected by Direct Electrochemistry

    PubMed Central

    2016-01-01

    The methylthiotransferases (MTTases) represent a subfamily of the S-adenosylmethionine (AdoMet) radical superfamily of enzymes that catalyze the attachment of a methylthioether (-SCH3) moiety on unactivated carbon centers. These enzymes contain two [4Fe-4S] clusters, one of which participates in the reductive fragmentation of AdoMet to generate a 5′-deoxyadenosyl 5′-radical and the other of which, termed the auxiliary cluster, is believed to play a central role in constructing the methylthio group and attaching it to the substrate. Because the redox properties of the bound cofactors within the AdoMet radical superfamily are so poorly understood, we have examined two MTTases in parallel, MiaB and RimO, using protein electrochemistry. We resolve the redox potentials of each [4Fe-4S] cluster, show that the auxiliary cluster has a potential higher than that of the AdoMet-binding cluster, and demonstrate that upon incubation of either enzyme with AdoMet, a unique low-potential state of the enzyme emerges. Our results are consistent with a mechanism whereby the auxiliary cluster is transiently methylated during substrate methylthiolation. PMID:27598886

  6. Electrochemistry "Discovery" Course for Undergraduates

    NASA Astrophysics Data System (ADS)

    May, Michael Alan; Gupta, Vijay K.

    1997-07-01

    We developed a chemistry selected topics course at Central State University, "Introduction to Laboratory Techniques in Electrochemistry" to: (1) give undergraduates hands-on experience with electrochemical measurements, (2) prepare students for summer research in Fuel Cell and Battery technology. Since students "learn by doing", the course is suitable for undergraduates from sophomore to senior levels. Students complete 6 laboratories, based on a "less is more" philosophy which emphasizes analytic and creative process rather than mandatory topical coverage. Eight electrochemical experiments are available: Construction of Zinc-Copper battery stacks, Lead Acid Battery discharge-charge cycles, Conductimetric titration of aspirin with Ammonium Hydroxide, Ion Selective Electrode determination of Fluoride in water, Cyclic Voltammetry of Potassium Ferricyanide solution, Cyclic Voltammetry of Sulfuric acid on Platinum working electrode, Anodic Stripping Voltammetry of Lead ion in solution, Differential Pulse Polarography of Lead ion in solution. Topics discussed in lecture include: chemical definitions, electrical definitions, Oxidation-Reduction reactions, Electrochemical series, Electrodes, Electrochemical Cells, direct Coulometry, electrolysis, electrochemical process efficiency, equilibrium Potentiometry, real Cell Voltages, Ion Selective Electrode types and designs, reference electrode designs, working electrode materials, pH buffers, Cyclic Voltammetry, Anodic Stripping Voltammetry, Polarography, differential pulse Polarography, and simple electrochemical instrumentation circuits.

  7. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-02-01

    This project seeks to advance the fundamental understanding of the physics-chemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid minedrainage. A novel approach to the study of pyrite aqueous electrochemistry is proposed, based on the use of both synthetic and natural ( i.e. coal-derived) pyrite specimens, the utilization of.pyrite both in the form of micro (i.e. colloidal and subcolloidal) and macro (i.e. rotating ring disk) electrodes, and the application of in-situ direct electroanalytical and spectroelectrochemical characterization techniques. The kinetic study of the reaction between sulfide and ferrous ions in solution suggested that the black species formed initially is FeHS[sup +] intermediate. To farther confirm this mechanism, the experiments aimed at establishing the stoichiometry for the intermediate were carried out thermodynamically with a stopped-flow spectrophotometric technique. The results showed that the mole ratio of H[sup [minus

  8. Fundamentals and applications of electrochemistry

    NASA Astrophysics Data System (ADS)

    McEvoy, A. J.

    2013-06-01

    The Voltaic pile, invented here on Lake Como 200 years ago, was a crucial step in the development of electrical engineering. For the first time a controlled and reliable source of electric current was available. The science of electrochemistry developed rapidly and is now a key contributor, not just to energy technology but also, for example, to metallurgy and industrial processes. The basic concepts of electrochemistry are presented, with the practical examples of its application in fuel cells, and with the perspective of the history of the subject.

  9. The birth of protein electrochemistry.

    PubMed

    Blanford, Christopher F

    2013-12-11

    The results from a final-year undergraduate project led to an $876M sale of a spin-out company 19 years later: the 1977 communication from Mark Eddowes and Allen Hill seeded the rich field of protein electrochemistry, the technology that underpins commercial glucose biosensors.

  10. The merger of electrochemistry and molecular electronics.

    PubMed

    McCreery, Richard L

    2012-02-01

    Molecular Electronics has the potential to greatly enhance existing silicon-based microelectronics to realize new functions, higher device density, lower power consumption, and lower cost. Although the investigation of electron transport through single molecules and molecular monolayers in "molecular junctions" is a recent development, many of the relevant concepts and phenomena are derived from electrochemistry, as practiced for the past several decades. The past 10+ years have seen an explosion of research activity directed toward how the structure of molecules affects electron transport in molecular junctions, with the ultimate objective of "rational design" of molecular components with new electronic functions, such as chemical sensing, interactions with light, and low-cost, low-power consumer electronics. In order to achieve these scientifically and commercially important objectives, the factors controlling charge transport in molecules "connected" to conducting contacts must be understood, and methods for massively parallel manufacturing of molecular circuits must be developed. This Personal Account describes the development of reproducible and robust molecular electronic devices, starting with modified electrodes used in electrochemistry and progressing to manufacturable molecular junctions. Although the field faced some early difficulties in reliability and characterization, the pieces are now in place for rapid advances in understanding charge transport at the molecular level. Inherent in the field of Molecular Electronics are many electrochemical concepts, including tunneling, redox exchange, activated electron transfer, and electron coupling between molecules and conducting contacts.

  11. Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in hybrid organic-inorganic film of chitosan/sol-gel/carbon nanotubes

    SciTech Connect

    Kang, Xinhuang; Wang, Jun; Tang, Zhiwen; Wu, Hong; Lin, Yuehe

    2009-04-15

    A hybrid organic-inorganic nanocomposite film of chitosan/sol-gel/multi-walled carbon nanotubes was constructed for the immobilization of horseradish peroxidase (HRP). This film was characterized by scanning electron microscopy. Direct electron transfer (DET) and bioelectrocatalysis of HRP incorporated into the composite film were investigated. The results indicate that the film can provide a favorable microenvironment for HRP to perform DET on the surface of glassy carbon electrodes with a pair of quasi-reversible redox waves and to retain its bioelectrocatalytic activity toward hydrogen peroxide.

  12. Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs.

    PubMed

    Ruokolainen, Miina; Gul, Turan; Permentier, Hjalmar; Sikanen, Tiina; Kostiainen, Risto; Kotiaho, Tapio

    2016-02-15

    The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and 7-ethoxycoumarin with phase I metabolites of the same compounds produced in vitro by human liver microsomes (HLM). Reaction products were analysed by UHPLC-MS. TiO2 photocatalysis simulated the in vitro phase I metabolism in HLM more comprehensively than did EC-Fenton or EC. Even though TiO2 photocatalysis, EC-Fenton and EC do not allow comprehensive prediction of phase I metabolism, all three methods produce several important metabolites without the need for demanding purification steps to remove the biological matrix. Importantly, TiO2 photocatalysis produces aliphatic and aromatic hydroxylation products where direct EC fails. Furthermore, TiO2 photocatalysis is an extremely rapid, simple and inexpensive way to generate oxidation products in a clean matrix and the reaction can be simply initiated and quenched by switching the UV lamp on/off. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Equilibrium and kinetic behavior of Fe(CN)6(3-/4-) and cytochrome c in direct electrochemistry using a film electrode thin-layer transmission cell.

    PubMed

    Dai, Yingrui; Zheng, Yi; Swain, Greg M; Proshlyakov, Denis A

    2011-01-15

    We report on the design and performance of a thin-layer electrochemical cell optimized for use with optically transparent film electrodes in combination with UV/vis and IR transmission spectroscopic measurements. The cell allows for measurements under both aerobic and anaerobic conditions. The direct, unmediated electron transfer, as assessed by the current transient, and the corresponding optical response observed for the Fe(CN)(6)(3-/4-) couple were in good agreement with theoretical predictions for voltammetry and optical absorption by an analyte confined in a thin layer. Chronoamperometric and spectroscopic measurements of Fe(CN)(6)(3-/4-) on gold mesh electrode revealed fast kinetics strongly influenced by the electrolyte concentration. Maximal apparent rates exceeding 2 s(-1) in 1 M KCl were observed optically. The direct kinetic and thermodynamic behavior of cytochrome c was compared with several electrode materials using the cell. The results showed heme ligand-dependent changes in the protein-electrode interactions. Mid-UV/visible spectral changes upon redox transitions in native cytochrome c and its cyanide derivative, as well as dissociation of the ferrous cytochrome c-CN complex, are reported.

  14. Equilibrium and Kinetic Behavior of Fe(CN)63−/4− and Cytochrome c in Direct Electrochemistry Using a Film Electrode Thin-Layer Transmission Cell

    PubMed Central

    Dai, Yingrui; Zheng, Yi; Swain, Greg M.; Proshlyakov, Denis A.

    2010-01-01

    We report on the design and performance of a thin-layer electrochemical cell optimized for use with optically transparent film electrodes in combination with UV/Vis and IR transmission spectroscopic measurements. The cell allows for measurements under both aerobic and anaerobic conditions. The direct, unmediated electron transfer, as assessed by the current transient, and the corresponding optical response observed for the Fe(CN)63−/4− couple were in good agreement with theoretical predictions for voltammetry and optical absorption by an analyte confined in a thin layer. Chronoamperometric and spectroscopic measurements of Fe(CN)63−/4− on gold mesh electrode revealed fast kinetics strongly influenced by the electrolyte concentration. Maximal apparent rates exceeding 2 s-1 in 1 M KCl were observed optically. The direct kinetic and thermodynamic behavior of cytochrome c was compared with several electrode materials using the cell. The results showed heme ligand-dependent changes in the protein-electrode interactions. Mid-UV/Visible spectral changes upon redox transitions in native cytochrome c and its cyanide derivative, as well as dissociation of the ferrous cytochrome c - CN complex are reported. PMID:21166441

  15. 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.

  16. Factors that Prevent Learning in Electrochemistry

    ERIC Educational Resources Information Center

    Schmidt, Hans-Jurgen; Marohn, Annette; Harrison, Allan G.

    2007-01-01

    Electrochemistry plays an important role in curricula, textbooks, and in everyday life. The purpose of the present study was to identify and understand secondary-school students' problems in learning electrochemistry at an introductory chemistry level. The investigation covered four areas: (a) electrolytes, (b) transport of electric charges in…

  17. Factors that Prevent Learning in Electrochemistry

    ERIC Educational Resources Information Center

    Schmidt, Hans-Jurgen; Marohn, Annette; Harrison, Allan G.

    2007-01-01

    Electrochemistry plays an important role in curricula, textbooks, and in everyday life. The purpose of the present study was to identify and understand secondary-school students' problems in learning electrochemistry at an introductory chemistry level. The investigation covered four areas: (a) electrolytes, (b) transport of electric charges in…

  18. Coupling into the base pair stack is necessary for DNA-mediated electrochemistry.

    PubMed

    Gorodetsky, Alon A; Green, Omar; Yavin, Eylon; Barton, Jacqueline K

    2007-01-01

    The electrochemistry of DNA films modified with different redox probes linked to DNA through saturated and conjugated tethers was investigated. Experiments feature two redox probes bound to DNA on two surfaces: anthraquinone (AQ)-modified uridines incorporated into thiolated DNA on gold (Au) and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-modified uridines in pyrene-labeled DNA on highly oriented pyrolytic graphite (HOPG). The electrochemistry of these labels when incorporated into DNA has been examined in DNA films containing both well matched and mismatched DNA. DNA-mediated electrochemistry is found to be effective for the TEMPO probe linked with an acetylene linker but not for a saturated TEMPO connected through an ethylenediamine linker. For the AQ probe, DNA-mediated electrochemistry is found with an acetylene linker to uridine but not with an alkyl chain to the 5' terminus of the oligonucleotide. Large electrochemical signals and effective discrimination of intervening base mismatches are achieved for the probes connected through the acetylene linkages, while probes connected through saturated linkages exhibit small electrochemical signals associated only with direct surface to probe charge transfer and poor mismatch discrimination. Thus DNA electrochemistry with these probes is dramatically influenced by the chemical nature of their linkage to DNA. These results highlight the importance of effective coupling into the pi-stack for long-range DNA-mediated electrochemistry.

  19. Amperometric cholesterol biosensor based on the direct electrochemistry of cholesterol oxidase and catalase on a graphene/ionic liquid-modified glassy carbon electrode.

    PubMed

    Gholivand, Mohammad Bagher; Khodadadian, Mehdi

    2014-03-15

    Cholesterol oxidase (ChOx) and catalase (CAT) were co-immobilized on a graphene/ionic liquid-modified glassy carbon electrode (GR-IL/GCE) to develop a highly sensitive amperometric cholesterol biosensor. The H2O2 generated during the enzymatic reaction of ChOx with cholesterol could be reduced electrocatalytically by immobilized CAT to obtain a sensitive amperometric response to cholesterol. The direct electron transfer between enzymes and electrode surface was investigated by cyclic voltammetry. Both enzymes showed well-defined redox peaks with quasi-reversible behaviors. An excellent sensitivity of 4.163 mA mM(-1)cm(-2), a response time less than 6s, and a linear range of 0.25-215 μM (R(2)>0.99) have been observed for cholesterol determination using the proposed biosensor. The apparent Michaelis-Menten constant (KM(app)) was calculated to be 2.32 mM. The bienzymatic cholesterol biosensor showed good reproducibility (RSDs<5%) with minimal interference from the coexisting electroactive compounds such as ascorbic acid and uric acid. The CAT/ChOx/GR-IL/GCE showed excellent analytical performance for the determination of free cholesterol in human serum samples.

  20. Direct Electrochemistry of Hemoglobin Immobilized on a Functionalized Multi-Walled Carbon Nanotubes and Gold Nanoparticles Nanocomplex-Modified Glassy Carbon Electrode

    PubMed Central

    Hong, Jun; Zhao, Ying-Xue; Xiao, Bao-Lin; Moosavi-Movahedi, Ali Akbar; Ghourchian, Hedayatollah; Sheibani, Nader

    2013-01-01

    Direct electron transfer of hemoglobin (Hb) was realized by immobilizing Hb on a carboxyl functionalized multi-walled carbon nanotubes (FMWCNTs) and gold nanoparticles (AuNPs) nanocomplex-modified glassy carbon electrode. The ultraviolet-visible absorption spectrometry (UV-Vis), transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) methods were utilized for additional characterization of the AuNPs and FMWCNTs. The cyclic voltammogram of the modified electrode has a pair of well-defined quasi-reversible redox peaks with a formal potential of −0.270 ± 0.002 V (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer constant (ks) was evaluated to be 4.0 ± 0.2 s−1. The average surface concentration of electro-active Hb on the surface of the modified glassy carbon electrode was calculated to be 6.8 ± 0.3 × 10−10 mol cm−2. The cathodic peak current of the modified electrode increased linearly with increasing concentration of hydrogen peroxide (from 0.05 nM to 1 nM) with a detection limit of 0.05 ± 0.01 nM. The apparent Michaelis-Menten constant (Kmapp) was calculated to be 0.85 ± 0.1 nM. Thus, the modified electrode could be applied as a third generation biosensor with high sensitivity, long-term stability and low detection limit. PMID:23881129

  1. 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.

  2. Modified fractal iron oxide magnetic nanostructure: A novel and high performance platform for redox protein immobilization, direct electrochemistry and bioelectrocatalysis application.

    PubMed

    Bagheri, Hasan; Ranjbari, Elias; Amiri-Aref, Mohaddeseh; Hajian, Ali; Ardakani, Yalda Hosseinzadeh; Amidi, Salimeh

    2016-11-15

    A novel biosensing platform based on fractal-pattern of iron oxides magnetic nanostructures (FIOMNs) and mixed hemi/ad-micelle of sodium dodecyl sulfate (SDS) was designed for the magnetic immobilization of hemoglobin (Hb) at a screen printed carbon electrode (SPCE). The FIOMNs was successfully synthesized through hydrothermal approach and characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray diffraction (XRD). In order to provide guidelines for the mixed hemi/ad-micelle formation, zeta-potential isotherms were investigated. The construction steps of the biosensor were evaluated by electrochemical impedance spectroscopy, cyclic voltammetry and Fourier transform infrared spectroscopy. Direct electron transfer of Hb incorporated into the biocomposite film was realized with a pair of quasi-reversible redox peak at the formal potential of -0.355V vs. Ag/AgCl attributing to heme Fe(III)/Fe(II) redox couple. The results suggested that synergistic functions regarding to the hyper-branched and multidirectional structure of FIOMNs and the dual interaction ability of mixed hemi/ad-micelle array of SDS molecules not only induce an effective electron transfer between the Hb and the underlying electrode (high heterogeneous electron transfer rate constant of 2.08s(-1)) but also provide powerful and special microenvironment for the adsorption of the redox proteins. Furthermore, the biosensor displayed an excellent performance to the electrocatalytic reduction of H2O2 with a detection limit of 0.48µM and Michaelis-Menten constant (Km) value of 44.2µM. The fabricated biosensor represented the features of sensitivity, disposable design, low sample volume, rapid and simple preparation step, and acceptable anti-interferences, which offer great perspectives for the screen-determination of H2O2 in real samples.

  3. Direct Electrochemistry and Electrocatalysis of Horseradish Peroxidase Immobilized in a DNA/Chitosan-Fe₃O₄ Magnetic Nanoparticle Bio-Complex Film.

    PubMed

    Gu, Tingting; Wang, Jianli; Xia, Hongqi; Wang, Si; Yu, Xiaoting

    2014-02-11

    A DNA/chitosan-Fe₃O₄ magnetic nanoparticle bio-complex film was constructed for the immobilization of horseradish peroxidase (HRP) on a glassy carbon electrode. HRP was simply mixed with DNA, chitosan and Fe₃O₄ nanoparticles, and then applied to the electrode surface to form an enzyme-incorporated polyion complex film. Scanning electron microscopy (SEM) was used to study the surface features of DNA/chitosan/Fe₃O₄/HRP layer. The results of electrochemical impedance spectroscopy (EIS) show that Fe₃O₄ and enzyme were successfully immobilized on the electrode surface by the DNA/chitosan bio-polyion complex membrane. Direct electron transfer (DET) and bioelectrocatalysis of HRP in the DNA/chitosan/Fe₃O₄ film were investigated by cyclic voltammetry (CV) and constant potential amperometry. The HRP-immobilized electrode was found to undergo DET and exhibited a fast electron transfer rate constant of 3.7 s(-1). The CV results showed that the modified electrode gave rise to well-defined peaks in phosphate buffer, corresponding to the electrochemical redox reaction between HRP(Fe((III)())) and HRP(Fe((II))). The obtained electrode also displayed an electrocatalytic reduction behavior towards H₂O₂. The resulting DNA/chitosan/Fe₃O₄/HRP/glassy carbon electrode (GCE) shows a high sensitivity (20.8 A·cm(-2)·M(-1)) toward H₂O₂. A linear response to H₂O₂ measurement was obtained over the range from 2 µM to 100 µM (R² = 0.99) and an amperometric detection limit of 1 µM (S/N = 3). The apparent Michaelis-Menten constant of HRP immobilized on the electrode was 0.28 mM. Furthermore, the electrode exhibits both good operational stability and storage stability.

  4. Coupling Electrochemistry with Probe Electrospray Ionization Mass Spectrometry.

    PubMed

    Cai, Yi; Liu, Pengyuan; Held, Michael A; Dewald, Howard D; Chen, Hao

    2016-04-18

    A new coupling of electrochemistry with mass spectrometry (MS) using probe electrospray ionization (PESI) is presented. Due to the high salt tolerance of PESI, the detection of electrochemical reaction products in room-temperature ionic liquids (RTILs) is realized for the first time. Furthermore, PESI-MS allows the analysis of electrochemical reaction products on different or multiple electrode surfaces. In addition, peptides and proteins fractionated through isoelectric focusing (IEF) in the presence of an external electric field can also be directly analyzed by using PESI-MS, suggesting a new and rapid characterization means for the IEF technique. This study reveals the versatility of EC/PESI-MS, which could have an impact in electrochemistry and bioanalysis fields.

  5. Electrochemistry of lunar rocks

    NASA Technical Reports Server (NTRS)

    Lindstrom, D. J.; Haskin, L. A.

    1979-01-01

    Electrolysis of silicate melts has been shown to be an effective means of producing metals from common silicate materials. No fluxing agents need be added to the melts. From solution in melts of diopside (CaMgSi2O6) composition, the elements Si, Ti, Ni, and Fe have been reduced to their metallic states. Platinum is a satisfactory anode material, but other cathode materials are needed. Electrolysis of compositional analogs of lunar rocks initially produces iron metal at the cathode and oxygen gas at the anode. Utilizing mainly heat and electricity which are readily available from sunlight, direct electrolysis is capable of producing useful metals from common feedstocks without the need for expendable chemicals. This simple process and the products obtained from it deserve further study for use in materials processing in space.

  6. Medicinal electrochemistry: integration of electrochemistry, medicinal chemistry and computational chemistry.

    PubMed

    Almeida, M O; Maltarollo, V G; de Toledo, R A; Shim, H; Santos, M C; Honorio, K M

    2014-01-01

    Over the last centuries, there were many important discoveries in medicine that were crucial for gaining a better understanding of several physiological processes. Molecular modelling techniques are powerful tools that have been successfully used to analyse and interface medicinal chemistry studies with electrochemical experimental results. This special combination can help to comprehend medicinal chemistry problems, such as predicting biological activity and understanding drug action mechanisms. Electrochemistry has provided better comprehension of biological reactions and, as a result of many technological improvements, the combination of electrochemical techniques and biosensors has become an appealing choice for pharmaceutical and biomedical analyses. Therefore, this review will briefly outline the present scope and future advances related to the integration of electrochemical and medicinal chemistry approaches based on various applications from recent studies.

  7. An Effective Approach to Teaching Electrochemistry.

    ERIC Educational Resources Information Center

    Birss, Viola I.; Truax, D. Rodney

    1990-01-01

    An approach which may be useful for teaching electrochemistry in freshman college chemistry courses is presented. Discussed are the potential problems with teaching this subject and solutions provided by this approach. (CW)

  8. DNA Electrochemistry with Tethered Methylene Blue

    PubMed Central

    Pheeney, Catrina G.

    2012-01-01

    Methylene blue (MB′), covalently attached to DNA through a flexible C12 alkyl linker, provides a sensitive redox reporter in DNA electrochemistry measurements. Tethered, intercalated MB′ is reduced through DNA-mediated charge transport; the incorporation of a single base mismatch at position 3, 10, or 14 of a 17-mer causes an attenuation of the signal to 62 ± 3% of the well-matched DNA, irrespective of position in the duplex. The redox signal intensity for MB′–DNA is found to be least 3-fold larger than that of Nile blue (NB)–DNA, indicating that MB′ is even more strongly coupled to the π-stack. The signal attenuation due to an intervening mismatch does, however, depend on DNA film density and the backfilling agent used to passivate the surface. These results highlight two mechanisms for reduction of MB′ on the DNA-modified electrode: reduction mediated by the DNA base pair stack and direct surface reduction of MB′ at the electrode. These two mechanisms are distinguished by their rates of electron transfer that differ by 20-fold. The extent of direct reduction at the surface can be controlled by assembly and buffer conditions. PMID:22512327

  9. Physical electrochemistry of nanostructured devices.

    PubMed

    Bisquert, Juan

    2008-01-07

    This Perspective reviews recent developments in experimental techniques and conceptual methods applied to the electrochemical properties of metal-oxide semiconductor nanostructures and organic conductors, such as those used in dye-sensitized solar cells, high-energy batteries, sensors, and electrochromic devices. The aim is to provide a broad view of the interpretation of electrochemical and optoelectrical measurements for semiconductor nanostructures (sintered colloidal particles, nanorods, arrays of quantum dots, etc.) deposited or grown on a conducting substrate. The Fermi level displacement by potentiostatic control causes a broad change of physical properties such as the hopping conductivity, that can be investigated over a very large variation of electron density. In contrast to traditional electrochemistry, we emphasize that in nanostructured devices we must deal with systems that depart heavily from the ideal, Maxwell-Boltzmann statistics, due to broad distributions of states (energy disorder) and interactions of charge carriers, therefore the electrochemical analysis must be aided by thermodynamics and statistical mechanics. We discuss in detail the most characteristic densities of states, the chemical capacitance, and the transport properties, specially the chemical diffusion coefficient, mobility, and generalized Einstein relation.

  10. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1992-01-01

    Pyrite synthesis is of interest in many diverse fields, such as geology, fuel processing technology, chemistry, metallurgy, materials science, and so on. Based on fundamental studies of this process, the formation mechanisms of this important sulfide on the earth can be better understood. The studies can also help us to better understand the surface chemistry and electrochemistry of pyrite, thereby assisting in the development of more efficient processes for removal of the sulfide from coal. The work performed during this quarter focuses on the study of the reaction between aqueous sulfide ions and dissolved Fe(II) salts by using a stopped-flow spectrophotometric technique. At a wavelength of 500 mn, no absorption was observed with either aqueous sulfide or dissolved Fe(II) salt alone. However, when the two solutions were mixed, a strong absorbance appeared at the same wavelength. The absorbance-time curve showed that a black material formed at the first few seconds of the reaction, then this material decayed and changed gradually to a lighter dark material within the following several minutes. These processes were pH-dependent. It was more likely to form the black intermediate at the pH range from 7 to 8. This indicates that the reaction between Fe[sup 2+] and HS[sup [minus

  11. The electrochemistry of nanostructured titanium dioxide electrodes.

    PubMed

    Berger, Thomas; Monllor-Satoca, Damián; Jankulovska, Milena; Lana-Villarreal, Teresa; Gómez, Roberto

    2012-08-27

    Several of the multiple applications of titanium dioxide nanomaterials are directly related to the introduction or generation of charge carriers in the oxide. Thus, electrochemistry plays a central role in the understanding of the factors that must be controlled for the optimization of the material for each application. Herein, the main conceptual tools needed to address the study of the electrochemical properties of TiO(2) nanostructured electrodes are reviewed, as well as the electrochemical methods to prepare and modify them. Particular attention is paid to the dark electrochemical response of these nanomaterials and its direct connection with the TiO(2) electronic structure, interfacial area and grain boundary density. The physical bases for the generation of currents under illumination are also presented. Emphasis is placed on the fact that the kinetics of charge-carrier transfer to solution determines the sign and value of the photocurrent. Furthermore, methods for extracting kinetic information from open-circuit potential and photocurrent measurements are briefly presented. Some aspects of the combination of electrochemical and spectroscopic measurements are also dealt with. Finally, some of the applications of TiO(2) nanostructured samples derived from their electrochemical properties are concisely reviewed. Particular attention is paid to photocatalytic processes and, to a lesser extent, to photosynthetic reactions as well as to applications related to energy from the aspects of both saving (electrochromic layers) and accumulation (batteries). The use of TiO(2) nanomaterials in solar cells is not covered, as a number of reviews have been published addressing this issue. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Graphene-based nanomaterials and their electrochemistry.

    PubMed

    Pumera, Martin

    2010-11-01

    Graphene-based nanomaterials are in the forefront of chemical research. This tutorial review provides an introduction to their electrochemistry, its fundamentals and applications. Selected examples of applications in energy storage and sensing are presented. The synthetic methods for preparing graphenes as well as their materials chemistry are thoroughly discussed, as they have a profound influence on the electronic and electrochemical behavior of graphene-related nanomaterials. Inherent electrochemistry and spectroelectrochemistry of graphene nanomaterials is discussed thoroughly. Important application in sensing and energy storage areas are highlighted.

  13. Multiplexed Electrochemistry of DNA-bound Metalloproteins

    PubMed Central

    Pheeney, Catrina G.; Arnold, Anna R.; Grodick, Michael A.; Barton, Jacqueline K.

    2013-01-01

    Here we describe a multiplexed electrochemical characterization of DNA-bound proteins containing [4Fe-4S] clusters. DNA-modified electrodes have become an essential tool for the characterization of the redox chemistry of DNA repair proteins containing redox cofactors, and multiplexing offers a means to probe different complex samples and substrates in parallel to elucidate this chemistry. Multiplexed analysis of EndonucleaseIII (EndoIII), a DNA repair protein containing a [4Fe-4S] cluster known to be accessible via DNA-mediated charge transport, shows subtle differences in the electrochemical behavior as a function of DNA morphology. The peak splitting, signal broadness, sensitivity to π-stack perturbations, and kinetics were all characterized for the DNA-bound reduction of EndoIII on both closely and loosely packed DNA films. DNA-bound EndoIII is seen to have two different electron transfer pathways for reduction, either through the DNA base stack or through direct surface reduction; closely packed DNA films, where the protein has limited surface accessibility, produce electrochemical signals reflecting electron transfer that is DNA-mediated. Multiplexing furthermore permits the comparison of the electrochemistry of EndoIII mutants, including a new family of mutations altering the electrostatics surrounding the [4Fe-4S] cluster. While little change in the midpoint potential was found for this family of mutants, significant variations in the efficiency of DNA-mediated electron transfer were apparent. Based on the stability of these proteins, examined by circular dichroism, we propose that the electron transfer pathway can be perturbed not only by the removal of aromatic residues but also through changes in solvation near the cluster. PMID:23899026

  14. Electrochemistry in the General Chemistry Curriculum.

    ERIC Educational Resources Information Center

    Chambers, James Q.

    1983-01-01

    Outlines several ideas on introductory electrochemistry material suitable for college-level general chemistry. These include discussions of conductivity in solids and electrolytes, electrical quantities/properties, electrode potentials, and membrane potentials. Indicates that whatever strategy is used to present this material, the presentation…

  15. A Tape-Lecture Course in Electrochemistry.

    ERIC Educational Resources Information Center

    Sheridan, P.

    1978-01-01

    Investigates the possibility of using audio-tapes for self-study courses in technical colleges. This article presents: (1) description of the electrochemistry course taught; (2) results of the assessment of student reaction to the course; and (3) conclusions. (HM)

  16. Electrochemistry in the General Chemistry Curriculum.

    ERIC Educational Resources Information Center

    Chambers, James Q.

    1983-01-01

    Outlines several ideas on introductory electrochemistry material suitable for college-level general chemistry. These include discussions of conductivity in solids and electrolytes, electrical quantities/properties, electrode potentials, and membrane potentials. Indicates that whatever strategy is used to present this material, the presentation…

  17. Bipolar electrochemistry: from materials science to motion and beyond.

    PubMed

    Loget, Gabriel; Zigah, Dodzi; Bouffier, Laurent; Sojic, Neso; Kuhn, Alexander

    2013-11-19

    crucial aspect, as there is no directed motion without symmetry breaking. Controlling the motion of objects at the micro- and nanoscale is of primary importance for many potential applications, ranging from medical diagnosis to nanosurgery, and has generated huge interest in the scientific community in recent years. Several original approaches to design micro- and nanomotors have been explored, with propulsion strategies based on chemical fuelling or on external fields. The first strategy is using the asymmetric particles generated by bipolar electrodeposition and employing them directly as micromotors. We have demonstrated this by using the catalytic and magnetic properties of Janus objects. The second strategy is utilizing bipolar electrochemistry as a direct trigger of motion of isotropic particles. We developed mechanisms based on a simultaneous dissolution and deposition, or on a localized asymmetric production of bubbles. We then used these for the translation, the rotation and the levitation of conducting objects. These examples give insight into two interesting fields of applications of the concept of bipolar electrochemistry, and open perspectives for future developments in materials science and for generating motion at different scales.

  18. Investigating Nanoscale Electrochemistry with Surface- and Tip-Enhanced Raman Spectroscopy.

    PubMed

    Zaleski, Stephanie; Wilson, Andrew J; Mattei, Michael; Chen, Xu; Goubert, Guillaume; Cardinal, M Fernanda; Willets, Katherine A; Van Duyne, Richard P

    2016-09-20

    The chemical sensitivity of surface-enhanced Raman spectroscopy (SERS) methodologies allows for the investigation of heterogeneous chemical reactions with high sensitivity. Specifically, SERS methodologies are well-suited to study electron transfer (ET) reactions, which lie at the heart of numerous fundamental processes: electrocatalysis, solar energy conversion, energy storage in batteries, and biological events such as photosynthesis. Heterogeneous ET reactions are commonly monitored by electrochemical methods such as cyclic voltammetry, observing billions of electrochemical events per second. Since the first proof of detecting single molecules by redox cycling, there has been growing interest in examining electrochemistry at the nanoscale and single-molecule levels. Doing so unravels details that would otherwise be obscured by an ensemble experiment. The use of optical spectroscopies, such as SERS, to elucidate nanoscale electrochemical behavior is an attractive alternative to traditional approaches such as scanning electrochemical microscopy (SECM). While techniques such as single-molecule fluorescence or electrogenerated chemiluminescence have been used to optically monitor electrochemical events, SERS methodologies, in particular, have shown great promise for exploring electrochemistry at the nanoscale. SERS is ideally suited to study nanoscale electrochemistry because the Raman-enhancing metallic, nanoscale substrate duly serves as the working electrode material. Moreover, SERS has the ability to directly probe single molecules without redox cycling and can achieve nanoscale spatial resolution in combination with super-resolution or scanning probe microscopies. This Account summarizes the latest progress from the Van Duyne and Willets groups toward understanding nanoelectrochemistry using Raman spectroscopic methodologies. The first half of this Account highlights three techniques that have been recently used to probe few- or single-molecule electrochemical

  19. Proximal bacterial lysis and detection in nanoliter wells using electrochemistry.

    PubMed

    Besant, Justin D; Das, Jagotamoy; Sargent, Edward H; Kelley, Shana O

    2013-09-24

    Rapid and direct genetic analysis of low numbers of bacteria using chip-based sensors is limited by the slow diffusion of mRNA molecules. Long incubation times are required in dilute solutions in order to collect a sufficient number of molecules at the sensor surface to generate a detectable signal. To overcome this barrier here we present an integrated device that leverages electrochemistry-driven lysis less than 50 μm away from electrochemical nucleic acid sensors to overcome this barrier. Released intracellular mRNA can diffuse the short distance to the sensors within minutes, enabling rapid and sensitive detection. We validate this strategy through direct lysis and detection of E. coli mRNA at concentrations as low as 0.4 CFU/μL in 2 min, a clinically relevant combination of speed and sensitivity for a sample-to-answer molecular analysis approach.

  20. Nano scale electrochemistry: Application to solid electrolytes

    NASA Astrophysics Data System (ADS)

    Lee, Minhwan

    Electrochemistry underlies a variety of useful applications such as batteries, fuel cells, and ionic sensors. However, these applications are currently facing numerous problems and challenges such as low power/energy density, short running time, low efficiency, vulnerability to contamination and costliness. The rate of improvement has recently decreased because the fundamental scientific understanding for each electrochemical phenomenon is limited. For the fundamental understanding of physics behind the observed bulk phenomena, direct nano-scale observation should be of great help. In the last few decades, a variety of scanning probe based nano-scale electrical/electrochemical measurement schemes has been developed. The first part of this thesis presents a newly proposed method to obtain AC impedance maps and its application to a few solid electrolytes. The Kelvin Probe Microscopy (KPM) and electrostatic force microscopy (EFM) were considered as alternative methods to investigate ionic systems. A series of surface potential maps could reveal the local distribution and movement of ionic species. However, the geometric convolution between the tip and the surface causes significant artifacts in surface potential measurement. A novel method for suppressing this artifact is presented in this thesis. For the KPM or EFM, due to the long range property of electrostatic interaction and the finite size of probe, the detected electric signal is obscured and subject to complicated interaction. For that reason, the modeling and analysis of these techniques is crucial to obtain accurate information. Numerical calculations using the boundary element method help to link the observed electrostatic signal with quantitative physical parameters. In addition, this simulation shows the impact of the feature size and the tip geometry on the experimental resolution and accuracy. Besides the "probing" or "characterizing" capability, a sharp tip enables highly accurate and nano

  1. Factors that prevent learning in electrochemistry

    NASA Astrophysics Data System (ADS)

    Schmidt, Hans-Jürgen; Marohn, Annette; Harrison, Allan G.

    2007-02-01

    Electrochemistry plays an important role in curricula, textbooks, and in everyday life. The purpose of the present study was to identify and understand secondary-school students' problems in learning electrochemistry at an introductory chemistry level. The investigation covered four areas: (a) electrolytes, (b) transport of electric charges in electrolyte solutions, (c) the anode and the cathode, and (d) the minus and plus poles. Written tests were given to high-school students in five cycles. The population from which random samples were drawn totalled 15,700 subjects. Students were asked to select the correct answers and to justify their choices. It was found that students based their reasoning on four alternative concepts: (a) During electrolysis, the electric current produces ions; (b) electrons migrate through the solution from one electrode to the other; (c) the cathode is always the minus pole, the anode the plus pole; and (d) the plus and minus poles carry charges. The results suggest a teaching strategy in which students first experience and learn about electrochemistry concepts. In the second step, appropriate concept terms are added, and students then are confronted with the alternative concepts described in this article.

  2. Electrochemistry of xanthine oxidase and its interaction with nitric oxide.

    PubMed

    Zhou, Hui; Xu, Yi; Chen, Ting; Suzuki, Iwao; Li, Genxi

    2006-02-01

    With the help of nanocrystalline TiO2, the direct electrochemistry of xanthine oxidase (XOD) was achieved and two pairs of redox waves were observed. The interaction between XOD and nitric oxide (NO) was also investigated. The experimental results reveal that NO can be reduced at a XOD-nano TiO2 film modified electrode. When the NO concentration was low, the reduced product, HNO, would inactivate the protein. However, when the NO concentration was high, HNO would continue to react with NO to form N2O2- and N3O3-, which would not inhibit XOD, and thus the amount of active protein did not decrease any further.

  3. Electrochemistry-mass spectrometry in drug metabolism and protein research.

    PubMed

    Permentier, Hjalmar P; Bruins, Andries P; Bischoff, Rainer

    2008-01-01

    The combination of electrochemistry coupled on-line to mass spectrometry (EC-MS) forms a powerful analytical technique with unique applications in the fields of drug metabolism and proteomics. In this review the latest developments are surveyed from both instrumental and application perspectives. The limitations and solutions for coupling an electrochemical system to a mass spectrometer are discussed. The electrochemical mimicking of drug metabolism, specifically by Cytochrome P450, is high-lighted as an application with high biomedical relevance. The EC-MS analysis of proteins also has promising new applications for both proteomics research and biomarker discovery. EC-MS has furthermore advantages for improved analyte detection with mass spectrometry, both for small molecules and large biomolecules. Finally, potential future directions of development of the technique are briefly discussed.

  4. ETUDE - European Trade Union Distance Education.

    ERIC Educational Resources Information Center

    Creanor, Linda; Walker, Steve

    2000-01-01

    Describes transnational distance learning activities among European trade union educators carried out as part of the European Trade Union Distance Education (ETUDE) project, supported by the European Commission. Highlights include the context of international trade union distance education; tutor training course; tutors' experiences; and…

  5. Centre National d'Etudes Spatiales

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2000-11-01

    The Centre National d'Etudes Spatiales (CNES) draws up, proposes and conducts France's space policy. Its role is to develop the uses of space, to meet the civilian and military needs of public bodies and of the scientific community, and to foster the development and dissemination of new applications, designed to create wealth and jobs....

  6. Development of an Electrochemistry Teaching Sequence Using a Phenomenographic Approach

    ERIC Educational Resources Information Center

    Rodriguez-Velazquez, Sorangel

    2013-01-01

    Electrochemistry is the area of chemistry that studies electron transfer reactions across an interface. Chemistry education researchers have acknowledged that difficulties in electrochemistry instruction arise due to the level of abstraction of the topic, lack of adequate explanations and representations found in textbooks, and a quantitative…

  7. Development of an Electrochemistry Teaching Sequence Using a Phenomenographic Approach

    ERIC Educational Resources Information Center

    Rodriguez-Velazquez, Sorangel

    2013-01-01

    Electrochemistry is the area of chemistry that studies electron transfer reactions across an interface. Chemistry education researchers have acknowledged that difficulties in electrochemistry instruction arise due to the level of abstraction of the topic, lack of adequate explanations and representations found in textbooks, and a quantitative…

  8. Electrochemistry-mass spectrometry for mechanism study of oxygen reduction at water/oil interface

    NASA Astrophysics Data System (ADS)

    Liu, Shu-Juan; Yu, Zheng-Wei; Qiao, Liang; Liu, Bao-Hong

    2017-04-01

    Electrochemistry methods have been widely employed in the development of renewable energy, and involved in various processes, e.g. water splitting and oxygen reduction. Remarkable progress notwithstanding, there are still many challenges in further optimization of catalysts to achieve high performance. For this purpose, an in-depth understanding of reaction mechanism is needed. In this study, an electrochemistry-mass spectrometry method based on a Y-shaped dual-channel microchip as electrochemical cell and ionization device was demonstrated. Combined solutions of aqueous phase and oil phase were introduced into mass spectrometer directly when electrochemical reactions were happening to study the reduction of oxygen by decamethylferrocene or tetrathiafulvalene under the catalysis of a metal-free porphyrin, tetraphenylporphyrin, at water/1,2-dichloroethane interfaces. Monoprotonated and diprotonated tetraphenylporphyrin were detected by mass spectrometer, confirming the previously proposed mechanism of the oxygen reduction reaction. This work offers a new approach to study electrochemical reactions at liquid-liquid interface.

  9. Electrochemistry at carbon nanotubes: perspective and issues.

    PubMed

    Dumitrescu, Ioana; Unwin, Patrick R; Macpherson, Julie V

    2009-12-07

    Electrochemistry at carbon nanotubes (CNTs) is a large and growing field, but one in which there is still uncertainty about the fundamental activity of CNTs as electrode materials. On the one hand, there are many reports which focus on the favourable electrochemical properties of CNT electrodes, such as enhanced detection sensitivity, electrocatalytic effects and reduced fouling. On the other hand, other studies suggest that CNTs may be no more electroactive than graphitic powder. Furthermore, it has been proposed that the catalytic nanoparticles from which CNTs are formed may dominate the electrochemical characteristics in some instances. A considerable body of the literature presumes that the CNT sidewall is inert and that edge-plane-graphite-like open ends and defect sites are responsible for the electron transfer activity observed. In contrast, studies of well characterised single-walled nanotube (SWNT) electrodes, either as individual tubes or as two-dimensional networks, suggest sidewall activity. This review highlights how the various discrepancies in CNT electrochemistry may have arisen, by taking a historical view of the field and identifying crucial issues that still need to be solved. When assessing the behaviour of CNT electrodes, it is vitally important that careful consideration is given to the type of CNT used (SWNT or multi-walled), the quality of the material (presence of impurities), the effect of chemical processing steps in the fabrication of electrodes and the experimental arrangements adopted. Understanding these key features is an essential requirement to develop a fundamental understanding of CNT electrochemistry, to allow a wide range of electroanalytical applications, and to move the field forward rationally. As part of this process, high resolution electrochemical and electrical imaging techniques are expected to play a significant role in the future, as well as theoretical developments which examine the fundamentals of electron transfer

  10. NASA Glenn Research Center Electrochemistry Branch Overview

    NASA Technical Reports Server (NTRS)

    Manzo, Michelle A.; Hoberecht, Mark; Reid, Concha

    2010-01-01

    This presentation covers an overview of NASA Glenn's history and heritage in the development of electrochemical systems for aerospace applications. Current programs related to batteries and fuel cells are addressed. Specific areas of focus are Li-ion batteries and Polymer Electrolyte Membrane Fuel cells systems and their development for future Exploration missions. The presentation covers details of current component development efforts for high energy and ultra high energy Li-ion batteries and non-flow-through fuel cell stack and balance of plant development. Electrochemistry Branch capabilities and facilities are also addressed.

  11. Electrochemistry of Carbon Dioxide on Carbon Electrodes.

    PubMed

    Yang, Nianjun; Waldvogel, Siegfried R; Jiang, Xin

    2016-01-04

    Carbon electrodes have the advantages of being chemically inert at negative potential ranges in all media and high offset potentials for hydrogen evolution in comparison to metal electrodes, and therefore are the most suitable electrodes for electrochemistry and electrochemical conversion of CO2 into valuable chemicals. Herein we summarize on carbon electrodes the voltammetry, electrochemical and electrocatalytic CO2 reduction, as well as electron synthesis using CO2 and carbon electrodes. The electrocatalytic CO2 reduction using carbocatalyts and the future activities about electrochemical CO2 conversion are highlighted.

  12. Electrochemistry of Main-Group Phthalocyanines.

    DTIC Science & Technology

    1981-07-30

    to follow a linear relationship with the function r/(ze) (radius/charge). This reltionshlp may be used to facilitate the design of photocatalysts with...ze) and a function of central metal ion has been published. We have recently completed a study of the electrochemistry of main- us n i. Figure I for...SiV 54 0.074 -540 CIA 111 67.5 0.044 915 -655 1570Experimental Secfio* CiGat el 76 0.040 865 -735 1600Clintl! 94 0.032 830 -715 1545The r.-:m grUp

  13. Electrochemistry in the mimicry of oxidative drug metabolism by cytochrome P450s.

    PubMed

    Nouri-Nigjeh, Eslam; Bischoff, Rainer; Bruins, Andries P; Permentier, Hjalmar P

    2011-05-01

    Prediction of oxidative drug metabolism at the early stages of drug discovery and development requires fast and accurate analytical techniques to mimic the in vivo oxidation reactions by cytochrome P450s (CYP). Direct electrochemical oxidation combined with mass spectrometry, although limited to the oxidation reactions initiated by charge transfer, has shown promise in the mimicry of certain CYP-mediated metabolic reactions. The electrochemical approach may further be utilized in an automated manner in microfluidics devices facilitating fast screening of oxidative drug metabolism. A wide range of in vivo oxidation reactions, particularly those initiated by hydrogen atom transfer, can be imitated through the electrochemically-assisted Fenton reaction. This reaction is based on O-O bond activation in hydrogen peroxide and oxidation by hydroxyl radicals, wherein electrochemistry is used for the reduction of molecular oxygen to hydrogen peroxide, as well as the reduction of Fe(3+) to Fe(2+). Metalloporphyrins, as surrogates for the prosthetic group in CYP, utilizing metallo-oxo reactive species, can also be used in combination with electrochemistry. Electrochemical reduction of metalloporphyrins in solution or immobilized on the electrode surface activates molecular oxygen in a manner analogous to the catalytical cycle of CYP and different metalloporphyrins can mimic selective oxidation reactions. Chemoselective, stereoselective, and regioselective oxidation reactions may be mimicked using electrodes that have been modified with immobilized enzymes, especially CYP itself. This review summarizes the recent attempts in utilizing electrochemistry as a versatile analytical and preparative technique in the mimicry of oxidative drug metabolism by CYP.

  14. A new strategy for achieving vertically-erected and hierarchical TiO2 nanosheets array/carbon cloth as a binder-free electrode for protein impregnation, direct electrochemistry and mediator-free glucose sensing.

    PubMed

    Liu, Jing; He, Ziming; Khoo, Si Yun; Tan, Timothy Thatt Yang

    2016-03-15

    We present a new approach to directly grow uniform and highly-ordered TiO2 nanosheets array (NSA) on a low-cost flexible carbon cloth substrate while simultaneously fulfill precise TiO2 nanostructure tailoring and crystal phase control. The unique vertically-erected TiO2 NSA/carbon cloth with hierarchical structures was directly explored as electrode for enzyme immobilization and biosensing applications without suffering any influences of insulating binders usually used to fix nanomaterials on conductive substrates during sensor fabrications. Efficient direct electron transfer was successfully achieved for glucose oxidase (GOx) immobilized on the TiO2 NSA/carbon cloth, which produces a stable, mediator-free glucose sensor with good selectivity, high-sensitivity (52 μA mM(-1)cm(-2)), low response time (<5s) and low detection limit (23.4 μM, S/N=3). The mechanism of the superior direct electrochemical properties and sensing performance was investigated in detail, and discussed from the aspects of material nanostructure and crystalline form of TiO2 NSA, and an intimate contact between TiO2 and carbon cloth resulted from direct crystallization and growth of TiO2 nanosheets on the substrate.

  15. Analytical Electrochemistry: Methodology and Applications of Dynamic Techniques.

    ERIC Educational Resources Information Center

    Heineman, William R.; Kissinger, Peter T.

    1980-01-01

    Reports developments involving the experimental aspects of finite and current analytical electrochemistry including electrode materials (97 cited references), hydrodynamic techniques (56), spectroelectrochemistry (62), stripping voltammetry (70), voltammetric techniques (27), polarographic techniques (59), and miscellany (12). (CS)

  16. Analytical Electrochemistry: Theory and Instrumentation of Dynamic Techniques.

    ERIC Educational Resources Information Center

    Johnson, Dennis C.

    1980-01-01

    Emphasizes trends in the development of six topics concerning analytical electrochemistry, including books and reviews (34 references cited), mass transfer (59), charge transfer (25), surface effects (33), homogeneous reactions (21), and instrumentation (31). (CS)

  17. Analytical Electrochemistry: Theory and Instrumentation of Dynamic Techniques.

    ERIC Educational Resources Information Center

    Johnson, Dennis C.

    1980-01-01

    Emphasizes trends in the development of six topics concerning analytical electrochemistry, including books and reviews (34 references cited), mass transfer (59), charge transfer (25), surface effects (33), homogeneous reactions (21), and instrumentation (31). (CS)

  18. Analytical Electrochemistry: Methodology and Applications of Dynamic Techniques.

    ERIC Educational Resources Information Center

    Heineman, William R.; Kissinger, Peter T.

    1980-01-01

    Reports developments involving the experimental aspects of finite and current analytical electrochemistry including electrode materials (97 cited references), hydrodynamic techniques (56), spectroelectrochemistry (62), stripping voltammetry (70), voltammetric techniques (27), polarographic techniques (59), and miscellany (12). (CS)

  19. Electrochemistry of metalloproteins: protein film electrochemistry for the study of E. coli [NiFe]-hydrogenase-1.

    PubMed

    Evans, Rhiannon M; Armstrong, Fraser A

    2014-01-01

    Protein film electrochemistry is a technique which allows the direct control of redox-active enzymes, providing particularly detailed information on their catalytic properties. The enzyme is deposited onto a working electrode tip, and through control of the applied potential the enzyme activity is monitored as electrical current, allowing for direct study of inherent activity as electrons are transferred to and from the enzyme redox center(s). No mediators are used. Because the only enzyme present in the experiment is bound at the electrode surface, gaseous and liquid phase inhibitors can be introduced and removed whilst the enzyme remains in situ. Potential control means that kinetics and thermodynamics are explored simultaneously; the kinetics of a reaction can be studied as a function of potential. Steady-state catalytic rates are observed directly as current (for a given potential) and non-steady-state rates (such as interconversions between different forms of the enzyme) are observed from the change in current with time. The more active the enzyme, the higher the current and the better the signal-to-noise. In this chapter we outline the practical aspects of PFE for studying electroactive enzymes, using the Escherichia coli [NiFe]-hydrogenase 1 (Hyd-1) as an example.

  20. Electrochemistry-based Battery Modeling for Prognostics

    NASA Technical Reports Server (NTRS)

    Daigle, Matthew J.; Kulkarni, Chetan Shrikant

    2013-01-01

    Batteries are used in a wide variety of applications. In recent years, they have become popular as a source of power for electric vehicles such as cars, unmanned aerial vehicles, and commericial passenger aircraft. In such application domains, it becomes crucial to both monitor battery health and performance and to predict end of discharge (EOD) and end of useful life (EOL) events. To implement such technologies, it is crucial to understand how batteries work and to capture that knowledge in the form of models that can be used by monitoring, diagnosis, and prognosis algorithms. In this work, we develop electrochemistry-based models of lithium-ion batteries that capture the significant electrochemical processes, are computationally efficient, capture the effects of aging, and are of suitable accuracy for reliable EOD prediction in a variety of usage profiles. This paper reports on the progress of such a model, with results demonstrating the model validity and accurate EOD predictions.

  1. Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

    SciTech Connect

    Lines, Amanda M.; Wang, Zheming; Clark, Sue B.; Bryan, Samuel A.

    2016-05-04

    Fast, cost effective, and robust means of detecting and quantifying lanthanides are needed for supporting more efficient tracking within the nuclear, medicinal, and industrial fields. Spectroelectrochemistry (SEC) is a powerful technique combining electrochemistry and spectroscopy that can meet those needs. The primary limitation of SEC as a detection method for lanthanides is their low molar absorptivity in absorbance based measurements and low emission intensities in fluorescence based measurements; both lead to high limits of detection. These limitations can be circumvented by complexing the lanthanides with sensitizing ligands that enhance fluorescence, thereby dropping the limits of detection. Complexation may also stabilize the metal ions in solution and improve the electrochemical reversibility, or Nernstian behavior, of the redox couples. To demonstrate this concept, studies were completed using europium in complexes with four different sensitizing ligands. Initial work indicates Eu in the four complexes studied does display the necessary characteristics for SEC analysis, which was successfully and reproducibly applied to all Eu complexes.

  2. Graphene and its electrochemistry - an update.

    PubMed

    Ambrosi, Adriano; Chua, Chun Kiang; Latiff, Naziah Mohamad; Loo, Adeline Huiling; Wong, Colin Hong An; Eng, Alex Yong Sheng; Bonanni, Alessandra; Pumera, Martin

    2016-05-07

    The electrochemistry of graphene and its derivatives has been extensively researched in recent years. In the aspect of graphene preparation methods, the efficiencies of the top-down electrochemical exfoliation of graphite, the electrochemical reduction of graphene oxide and the electrochemical delamination of CVD grown graphene, are currently on par with conventional procedures. Electrochemical analysis of graphene oxide has revealed an unexpected inherent redox activity with, in some cases, an astonishing chemical reversibility. Furthermore, graphene modified with p-block elements has shown impressive electrocatalytic performances in processes which have been historically dominated by metal-based catalysts. Further progress has also been achieved in the practical usage of graphene in sensing and biosensing applications. This review is an update of our previous article in Chem. Soc. Rev. 2010, 39, 4146-4157, with special focus on the developments over the past two years.

  3. Mixed hemi/ad-micelles coated magnetic nanoparticles for the entrapment of hemoglobin at the surface of a screen-printed carbon electrode and its direct electrochemistry and electrocatalysis.

    PubMed

    Amiri-Aref, Mohaddeseh; Raoof, Jahan Bakhsh; Kiekens, Filip; De Wael, Karolien

    2015-12-15

    An efficient procedure for the physical entrapment of proteins within a biocompatible matrix and their immobilization on electrode surfaces is of utmost importance in the fabrication of biosensors. In this work, the magnetic entrapment of hemoglobin (Hb) at the surface of a screen-printed carbon electrode (SPCE), through mixed hemi/ad-micelles (MHAM) array of positively charged surfactant supported iron oxide magnetic nanoparticles (Mag-NPs), is reported. The Hb/MHAM@Mag-NPs biocomposite is captured at SPCE by a super magnet (Hb/MHAM@Mag-NPs/SPCE). To gain insight in the configuration of the mixed hemi/ad-micelles of CTAB at Mag-NPs, zeta-potential measurements were performed. The entrapment of Hb at MHAM@Mag-NPs was confirmed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Fourier transform infrared spectroscopy (FT-IR). Direct electron transfer of the Hb intercalated into the composite film showed a pair of well-defined quasi-reversible redox peak at formal potential of -0.255 V vs. Ag/AgCl corresponding to heme Fe(III)/Fe(II) redox couple. It shows that the MHAM@Mag-NPs composite could increase the adsorption ability for Hb, thus provides a facile direct electron transfer between the Hb and the substrate. The proposed biosensor showed excellent electrocatalytic activity to the H2O2 reduction in the wide concentration range from 5.0 to 300.0 µM obtained by amperometric measurement. The Michaelis-Menten constant (Km) value of Hb at the modified electrode is 55.4 µM, showing its high affinity. Magnetic entrapment offers a promising design for fast, convenient and effective immobilization of protein within a few minutes for determination of the target molecule in low sample volume at disposable cost-effective SPCE.

  4. Molybdenum, molybdenum oxides, and their electrochemistry.

    PubMed

    Saji, Viswanathan S; Lee, Chi-Woo

    2012-07-01

    The electrochemical behaviors of molybdenum and its oxides, both in bulk and thin film dimensions, are critical because of their widespread applications in steels, electrocatalysts, electrochromic materials, batteries, sensors, and solar cells. An important area of current interest is electrodeposited CIGS-based solar cells where a molybdenum/glass electrode forms the back contact. Surprisingly, the basic electrochemistry of molybdenum and its oxides has not been reviewed with due attention. In this Review, we assess the scattered information. The potential and pH dependent active, passive, and transpassive behaviors of molybdenum in aqueous media are explained. The major surface oxide species observed, reversible redox transitions of the surface oxides, pseudocapacitance and catalytic reduction are discussed along with carefully conducted experimental results on a typical molybdenum glass back contact employed in CIGS-based solar cells. The applications of molybdenum oxides and the electrodeposition of molybdenum are briefly reviewed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. The Mesoscopic Electrochemistry of Molecular Junctions

    PubMed Central

    Bueno, Paulo R.; Benites, Tiago A.; Davis, Jason J.

    2016-01-01

    Within the context of an electron dynamic (time-dependent) perspective and a voltage driving force acting to redistribute electrons between metallic and addressable molecular states, we define here the associated electron admittance and conductance. We specifically present a mesoscopic approach to resolving the electron transfer rate associated with the electrochemistry of a redox active film tethered to metallic leads and immersed in electrolyte. The methodology is centred on aligning the lifetime of the process of electron exchange with associated resistance and capacitance quantities. Notably, however, these are no longer those empirically known as charge transfer resistance and pseudo-capacitance, but are those derived instead from a consideration of the quantum states contained in molecular films and their accessibility through a scattering region existing between them and the metallic probe. The averaged lifetime (τr) associated with the redox site occupancy is specifically dependent on scattering associated with the quantum channels linking them to the underlying metallic continuum and associated with both a quantum resistance (Rq) and an electrochemical (redox) capacitance (Cr). These are related to electron transfer rate through k = 1/τr = (RqCr)−1. The proposed mesoscopic approach is consistent with Marcus’s (electron transfer rate) theory and experimental measurements obtained by capacitance spectroscopy. PMID:26757677

  6. Janus Electrochemistry: Asymmetric Functionalization in One Step.

    PubMed

    Ibañez, David; Valles, Elisa; Gomez, Elvira; Colina, Alvaro; Heras, Aranzazu

    2017-09-29

    Janus structures represent an overwhelming member of materials with adaptable chemical and physical properties. Development of new synthesis routes has allowed the fabrication of Janus architectures with specific characteristics depending on the final applications. In the case of the membranes, the improvement of wet routes has been limited to the capillary effect, in which the solution can gradually penetrate through the membrane, avoiding a double modification different at each face of the membrane. In this work, we propose a new electrochemical methodology to circumvent the capillary limitation and obtain a double electrochemical functionalization in only one step in a controlled way. This innovative methodology has been validated using a tridirectional spectroelectrochemistry setup. Moreover, the information provided by this optical arrangement should be especially useful for the study of the different processes (ion transfer, assisted ion transfer, and electron transfer) that can take place at liquid/liquid interfaces. Janus electrochemistry allows us to modify the two faces of a free-standing single-walled carbon nanotube electrode in a single experiment. As proof of concept, the free-standing films have been functionalized with two different conducting polymers, polyaniline and poly(3-hexylthiophene), in one electrochemical experiment. According to the obtained results, this new electrochemical methodology will open new gates for the design and functionalization of Janus materials.

  7. Direct electrochemistry of porcine purple acid phosphatase (uteroferrin).

    PubMed

    Bernhardt, Paul V; Schenk, Gerhard; Wilson, Gregory J

    2004-08-17

    Cyclic voltammetry of the non-heme diiron enzyme porcine purple acid phosphatase (uteroferrin, Uf) has been reported for the first time. Totally reversible one-electron oxidation responses (FeIII-FeII --> FeII-FeIII) are seen both in the absence and in the presence of weak competitive inhibitors phosphate and arsenate, and dissociation constants of these oxoanion complexes formed with uteroferrin in its oxidized state (Uf(o)) have been determined. The effect of pH on the redox potentials has been investigated in the range 3 < pH < 6.5, enabling acid dissociation constants for Uf(o) and its phosphate and arsenate complexes to be calculated.

  8. Hollow spherical nanostructured polydiphenylamine for direct electrochemistry and glucose biosensor.

    PubMed

    Santhosh, P; Manesh, K M; Uthayakumar, S; Gopalan, A I; Lee, K-P

    2009-03-15

    Nanostructured, hollow spheres of polydiphenylamine (HS-PDPA) are prepared through a "soft template assisted self-assembly" approach. An enzymatic glucose biosensor is fabricated through immobilizing glucose oxidase (GOx) into HS-PDPA matrix. The HS-PDPA-GOx electrode exhibits a pair of well-defined reversible redox peaks with a fast heterogeneous electron transfer rate. At an applied potential of +0.65V, HS-PDPA-GOx electrode possesses high sensitivity (1.77 microAmM(-1)cm(-2)), stability and reproducibility towards glucose. The amperometric current response of HS-PDPA-GOx to glucose is linear in the concentration range between 1 and 28 mM with a detection limit of 0.05 mM (S/N=3). Also, HS-PDPA-GOx electrode shows high selectivity towards glucose in the presence of ascorbic acid, uric acid and acetaminophen at their maximum physiological concentrations.

  9. Shaping and exploring the micro- and nanoworld using bipolar electrochemistry.

    PubMed

    Loget, Gabriel; Kuhn, Alexander

    2011-06-01

    Bipolar electrochemistry is a technique with a rather young history in the field of analytical chemistry. Being based on the polarization of a conducting object which is exposed to an external electric field, it allowed recently the development of new methods for controlled surface modification at the micro- and nanoscale and very original analytical applications. Using bipolar electrodes, analyte separation and detection becomes possible based on miniaturized systems. Moreover, the modified objects that can be created with bipolar electrochemistry could find applications as key components for detection systems. In this contribution, the principles of bipolar electrochemistry will be reviewed, as well as recent developments that focus on the modification of objects at the nano- and microscale and their potential application in miniaturized analytical systems.

  10. Exploiting plug-and-play electrochemistry for drug discovery.

    PubMed

    Gao, Lixia; Teng, Yong

    2016-04-01

    Electrochemistry has emerged as a powerful analytical technique for chemical analysis of living cells, biologically active molecules and metabolites. Electrochemical biosensor, microfluidics and mass spectrometry are the most frequently used methods for electrochemical detection and monitory, which comprise a collection of extremely useful measurement tools for various fields of biology and medicine. Most recently, electrochemistry has been shown to be coupled with nanotechnology and genetic engineering to generate new enabling technologies, providing rapid, selective, and sensitive detection and diagnosis platforms. The primary focus of this review is to highlight the utility of electrochemical strategies and their conjunction with other approaches for drug metabolism and discovery. Current challenges and possible future developments and applications of electrochemistry in drug studies are also discussed.

  11. Workshop on the frontiers of theoretical and experimental electrochemistry

    SciTech Connect

    Gottesfeld, S.; Redondo, A.; Lemons, R.

    1986-01-01

    The Workshop on the Frontiers of Theoretical and Experimental Electrochemistry was held at the Los Alamos National Laboratory, February 25-26, 1985, to identify those problems and techniques that are at the forefront of electrochemistry research and to generate a summary that will be a guide to the most fruitful areas of electrochemistry research and a foundation for long-term support of such work in this country. Among the conclusions, major advances in understanding electrochemical systems are expected from the application of the new tools for in situ characterization of the solid/electrolyte interface. Parallel thrusts are needed in the areas of theory, experiments on well-defined surfaces, and exploratory research on new interfacial phenomena and new electrode materials. Several specific areas for new research are described in this report.

  12. Environmental electrochemistry: Fundamentals and applications in pollution abatement

    SciTech Connect

    Rajeshwar, K.; Ibanez, J.

    1996-12-31

    Electrochemistry is used both to detect and quantitatively analyze pollutants and to undertake the remediation of polluted environments. In these areas electrochemistry offers the advantages of detectability, selectivity, portability, and cost effectiveness. This book is a comprehensive review that covers a vast amount of territory, from basic electrochemical science to the use of commercially available remediation procedures. The first three chapters are introductory in nature. The subjects covered in chapters 4--7 include: electroanalytical techniques, electrochemical approaches to pollution abatement, photoelectrochemical methods for treating polluted air and water, and the disinfection of water.

  13. Electrochemistry, biosensors and microfluidics: a convergence of fields.

    PubMed

    Rackus, Darius G; Shamsi, Mohtashim H; Wheeler, Aaron R

    2015-08-07

    Electrochemistry, biosensors and microfluidics are popular research topics that have attracted widespread attention from chemists, biologists, physicists, and engineers. Here, we introduce the basic concepts and recent histories of electrochemistry, biosensors, and microfluidics, and describe how they are combining to form new application-areas, including so-called "point-of-care" systems in which measurements traditionally performed in a laboratory are moved into the field. We propose that this review can serve both as a useful starting-point for researchers who are new to these topics, as well as being a compendium of the current state-of-the art for experts in these evolving areas.

  14. Electrochemistry in Near-Critical and Supercritical Fluids. 6. The Electrochemistry of Ferrocene and Phenazine in Acetonitrile between 25C and 300C.

    DTIC Science & Technology

    1987-07-01

    electrochemical studies in near-critical CO2 with water. We describe here electrochemistry in the organic supercritical fluid acetonitrile (MeCN), where the...RESEARCH 1 FlE COP Contract NO0014- 84-K-0428 Task No. NR 051-693 TECHNICAL REPORT No. 8 (Electrochemistry in Near-Critical and Supercritical Fluids. 6. The...is suggested. FF V.. I r.M I- .- Electrochemistry in Near-Critical and Supercritical Fluids. 6. The Electrochemistry of Ferrocene and Phenazine in

  15. Chelating ionic liquids for reversible zinc electrochemistry.

    PubMed

    Kar, Mega; Winther-Jensen, Bjorn; Forsyth, Maria; MacFarlane, Douglas R

    2013-05-21

    Advanced, high energy-density, metal-air rechargeable batteries, such as zinc-air, are of intense international interest due to their important role in energy storage applications such as electric and hybrid vehicles, and to their ability to deal with the intermittency of renewable energy sources such as solar and wind. Ionic liquids offer a number of ideal thermal and physical properties as potential electrolytes in such large-scale energy storage applications. We describe here the synthesis and characterisation of a family of novel "chelating" ILs designed to chelate and solubilize the zinc ions to create electrolytes for this type of battery. These are based on quaternary alkoxy alkyl ammonium cations of varying oligo-ether side chains and anions such as p-toluene sulfonate, bis(trifluoromethylsulfonyl)amide and dicyanoamides. This work shows that increasing the ether chain length in the cation from two to four oxygens can increase the ionic conductivity and reduce the melting point from 67 °C to 15 °C for the tosylate system. Changing the anion also plays a significant role in the nature of the zinc deposition electrochemistry. We show that zinc can be reversibly deposited from [N(222(20201))][NTf2] and [N(222(202020201))][NTf2] beginning at -1.4 V and -1.7 V vs. SHE, respectively, but not in the case of tosylate based ILs. This indicates that the [NTf2] is a weaker coordinating anion with the zinc cation, compared to the tosylate anion, allowing the coordination of the ether chain to dominate the behavior of the deposition and stripping of zinc ions.

  16. Realtime structural electrochemistry of platinum clusters using dispersive XAFS

    SciTech Connect

    Allen, P.G.; Conradson, S.D.; Wilson, M.S.; Gottesfeld, S.; Raistrick, I.D.

    1993-12-31

    Chemical reference tables state that the standard potential for the reaction of Pt with water, Pt + 2H{sub 2}O {r_arrow} Pt(OH){sub 2} + 2H{sup +} + 2e{sup {minus}}, is 0.98 V, and electrochemical studies propose that this reaction may occur at potentials as low as 0.8 V. Using dispersive x-ray absorption fine-structure (XAFS) spectroscopy, the authors have directly probed the structural evolution of a Pt catalyst operating in-situ in a polymer electrolyte fuel cell during cyclic voltammetry. The changes in the number of Pt and O nearest-neighbors and the Pt charge demonstrate a close correspondence with features in the voltammogram. Because dispersive XAFS is very sensitive to detecting structural changes, they have been able to detect the presence of chemisorbed oxygen at potentials of 0.6--0.9 V in the anodic sweep. Since double-layer charging is regarded as the only process in this region for bulk Pt, these results may reflect a limitation of previous (indirect) studies on Pt electrochemistry, or they may indicate that these clusters are different from their bulk metal counterparts. Exploiting the time-resolving capability of dispersive XAFS, they also monitored changes in the Pt charge and the number of O and Pt nearest-neighbors during the electrochemical oxidation and reduction of the Pt clusters in real-time. The results are inconsistent with those expected from the place-exchange mechanism for the formation of the surface oxide on bulk Pt electrodes in aqueous solution; Pt{sub red} (k{sub 1}) {yields} Pt (submonolayer O)(k{sub 2}) {yields} PtO{sub x} (place exchanged Pt and O atoms: k{sub 1} >> k{sub 2}). Their current model for understanding these behaviors is that, relative to bulk Pt, unusual types of surface sites play a major role in determining the reactivity of these clusters.

  17. Understanding Electrochemistry Concepts Using the Predict-Observe-Explain Strategy

    ERIC Educational Resources Information Center

    Karamustafaoglu, Sevilay; Mamlok-Naaman, Rachel

    2015-01-01

    The current study deals with freshman students who study at the Department of Science at the Faculty of Education. The aim of the study was to investigate the effect of teaching electrochemistry concepts using Predict-Observe-Explain (POE) strategy. The study was quasi-experimental design using 20 students each in the experimental group (EG) and…

  18. Common Student Misconceptions in Electrochemistry: Galvanic, Electrolytic, and Concentration Cells.

    ERIC Educational Resources Information Center

    Sanger, Michael J.; Greenbowe, Thomas J.

    1997-01-01

    Investigates student (N=16) misconceptions concerning electrochemistry related to galvanic, electrolytic, and concentration cells. Findings indicate that most students demonstrating misconceptions were still able to calculate cell potentials correctly. Discusses common misconceptions and possible sources of these. Contains 33 references.…

  19. Facilitating Conceptual Change in Students' Understanding of Electrochemistry.

    ERIC Educational Resources Information Center

    Niaz, Mansoor

    2002-01-01

    Constructs a teaching strategy to facilitate conceptual change in freshman students' understanding of electrochemistry. Provides students with the correct response along with alternative responses (teaching experiments), producing a conflicting situation that is conducive to an equilibration of their cognitive structures. Concludes that the…

  20. LCEC: The Combination of Liquid Chromatography and Electrochemistry.

    ERIC Educational Resources Information Center

    Kissinger, Peter T.

    1983-01-01

    Use of combined liquid chromatography and finite-current electrochemistry (LCEC) procedures are discussed. Also discusses the relationship between electroactivity and molecular structure, selectivity in LCEC, and LCEC applications. Because of its selectivity and low detection limits, the procedures are most often applied in biomedical and…

  1. (The latest developments of the physical aspects of electrochemistry)

    SciTech Connect

    Liu, S.H.

    1990-09-24

    The author was one of 26 invited lecturers to discuss the latest developments of the physical aspects of electrochemistry. He interacted extensively with other lecturers and many participants from developing countries. He also visited with the Director of the Italian Synchrotron Radiation Source now under construction in Trieste, Italy.

  2. 2016 Electrochemistry Gordon Research Conference and Gordon Research Seminar

    DTIC Science & Technology

    2016-02-23

    Antibiotic Peptides Reconstituted into a Biomimetic Membrane Supported on Gold Electrodes" 8:20 pm - 8:35 pm Discussion 8:35 pm - 9:15 pm Andrea...34Semiconducting Colloidal TiO2 Nanoparticles During Photoxidation: Electrochemistry of Single Particles and Other Entities" 8:55 pm - 9:00 pm Discussion 9:00

  3. Understanding Electrochemistry Concepts Using the Predict-Observe-Explain Strategy

    ERIC Educational Resources Information Center

    Karamustafaoglu, Sevilay; Mamlok-Naaman, Rachel

    2015-01-01

    The current study deals with freshman students who study at the Department of Science at the Faculty of Education. The aim of the study was to investigate the effect of teaching electrochemistry concepts using Predict-Observe-Explain (POE) strategy. The study was quasi-experimental design using 20 students each in the experimental group (EG) and…

  4. Using a Teaching Model To Correct Known Misconceptions in Electrochemistry.

    ERIC Educational Resources Information Center

    Huddle, Penelope Ann; White, Margaret Dawn; Rogers, Fiona

    2000-01-01

    Describes a concrete teaching model designed to eliminate students' misconceptions about current flow in electrochemistry. The model uses a semi-permeable membrane rather than a salt bridge to complete the circuit and demonstrate the maintenance of cell neutrality. Concludes that use of the model led to improvement in students' understanding at…

  5. The 16th James L. Waters Annual Symposium: Electrochemistry

    NASA Astrophysics Data System (ADS)

    Michael, Adrian C.

    2007-04-01

    The 16th Annual James L. Waters Symposium focused on electrochemistry, with emphasis on methods involving the flow of current. The speakers in this year's symposium are uniquely qualified to review the history of electroanalytical chemistry starting with Heyrovsky's initial studies and culminating with the present state of the art. Each has contributed significantly to the scientific, technical, and commercial development of the field.

  6. Using a Teaching Model To Correct Known Misconceptions in Electrochemistry.

    ERIC Educational Resources Information Center

    Huddle, Penelope Ann; White, Margaret Dawn; Rogers, Fiona

    2000-01-01

    Describes a concrete teaching model designed to eliminate students' misconceptions about current flow in electrochemistry. The model uses a semi-permeable membrane rather than a salt bridge to complete the circuit and demonstrate the maintenance of cell neutrality. Concludes that use of the model led to improvement in students' understanding at…

  7. Common Student Misconceptions in Electrochemistry: Galvanic, Electrolytic, and Concentration Cells.

    ERIC Educational Resources Information Center

    Sanger, Michael J.; Greenbowe, Thomas J.

    1997-01-01

    Investigates student (N=16) misconceptions concerning electrochemistry related to galvanic, electrolytic, and concentration cells. Findings indicate that most students demonstrating misconceptions were still able to calculate cell potentials correctly. Discusses common misconceptions and possible sources of these. Contains 33 references.…

  8. Alleviating the Common Confusion Caused by Polarity in Electrochemistry.

    ERIC Educational Resources Information Center

    Moran, P. J.; Gileadi, E.

    1989-01-01

    Discussed is some of the confusion encountered in electrochemistry due to misunderstandings of sign conventions and simple mathematical errors. Clarified are issues involving emf series, IUPAC sign conventions, calculation of cell potentials, reference electrodes, the polarity of electrodes in electrochemical devices, and overpotential. (CW)

  9. Phase I and phase II reductive metabolism simulation of nitro aromatic xenobiotics with electrochemistry coupled with high resolution mass spectrometry.

    PubMed

    Bussy, Ugo; Chung-Davidson, Yu-Wen; Li, Ke; Li, Weiming

    2014-11-01

    Electrochemistry combined with (liquid chromatography) high resolution mass spectrometry was used to simulate the general reductive metabolism of three biologically important nitro aromatic molecules: 3-trifluoromethyl-4-nitrophenol (TFM), niclosamide, and nilutamide. TFM is a pesticide used in the Laurential Great Lakes while niclosamide and nilutamide are used in cancer therapy. At first, a flow-through electrochemical cell was directly connected to a high resolution mass spectrometer to evaluate the ability of electrochemistry to produce the main reduction metabolites of nitro aromatic, nitroso, hydroxylamine, and amine functional groups. Electrochemical experiments were then carried out at a constant potential of -2.5 V before analysis of the reduction products by LC-HRMS, which confirmed the presence of the nitroso, hydroxylamine, and amine species as well as dimers. Dimer identification illustrates the reactivity of the nitroso species with amine and hydroxylamine species. To investigate xenobiotic metabolism, the reactivity of nitroso species to biomolecules was also examined. Binding of the nitroso metabolite to glutathione was demonstrated by the observation of adducts by LC-ESI(+)-HRMS and the characteristics of their MSMS fragmentation. In conclusion, electrochemistry produces the main reductive metabolites of nitro aromatics and supports the observation of nitroso reactivity through dimer or glutathione adduct formation.

  10. Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.

    PubMed

    Cheng, Fangyi; Chen, Jun

    2012-03-21

    Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references).

  11. Strain Engineering to Modify the Electrochemistry of Energy Storage Electrodes

    PubMed Central

    Muralidharan, Nitin; Carter, Rachel; Oakes, Landon; Cohn, Adam P.; Pint, Cary L.

    2016-01-01

    Strain engineering has been a critical aspect of device design in semiconductor manufacturing for the past decade, but remains relatively unexplored for other applications, such as energy storage. Using mechanical strain as an input parameter to modulate electrochemical potentials of metal oxides opens new opportunities intersecting fields of electrochemistry and mechanics. Here we demonstrate that less than 0.1% strain on a Ni-Ti-O based metal-oxide formed on superelastic shape memory NiTi alloys leads to anodic and cathodic peak potential shifts by up to ~30 mV in an electrochemical cell. Moreover, using the superelastic properties of NiTi to enable strain recovery also recovers the electrochemical potential of the metal oxide, providing mechanistic evidence of strain-modified electrochemistry. These results indicate that mechanical energy can be coupled with electrochemical systems to efficiently design and optimize a new class of strain-modulated energy storage materials. PMID:27283872

  12. Strain Engineering to Modify the Electrochemistry of Energy Storage Electrodes.

    PubMed

    Muralidharan, Nitin; Carter, Rachel; Oakes, Landon; Cohn, Adam P; Pint, Cary L

    2016-06-10

    Strain engineering has been a critical aspect of device design in semiconductor manufacturing for the past decade, but remains relatively unexplored for other applications, such as energy storage. Using mechanical strain as an input parameter to modulate electrochemical potentials of metal oxides opens new opportunities intersecting fields of electrochemistry and mechanics. Here we demonstrate that less than 0.1% strain on a Ni-Ti-O based metal-oxide formed on superelastic shape memory NiTi alloys leads to anodic and cathodic peak potential shifts by up to ~30 mV in an electrochemical cell. Moreover, using the superelastic properties of NiTi to enable strain recovery also recovers the electrochemical potential of the metal oxide, providing mechanistic evidence of strain-modified electrochemistry. These results indicate that mechanical energy can be coupled with electrochemical systems to efficiently design and optimize a new class of strain-modulated energy storage materials.

  13. Strain Engineering to Modify the Electrochemistry of Energy Storage Electrodes

    NASA Astrophysics Data System (ADS)

    Muralidharan, Nitin; Carter, Rachel; Oakes, Landon; Cohn, Adam P.; Pint, Cary L.

    2016-06-01

    Strain engineering has been a critical aspect of device design in semiconductor manufacturing for the past decade, but remains relatively unexplored for other applications, such as energy storage. Using mechanical strain as an input parameter to modulate electrochemical potentials of metal oxides opens new opportunities intersecting fields of electrochemistry and mechanics. Here we demonstrate that less than 0.1% strain on a Ni-Ti-O based metal-oxide formed on superelastic shape memory NiTi alloys leads to anodic and cathodic peak potential shifts by up to ~30 mV in an electrochemical cell. Moreover, using the superelastic properties of NiTi to enable strain recovery also recovers the electrochemical potential of the metal oxide, providing mechanistic evidence of strain-modified electrochemistry. These results indicate that mechanical energy can be coupled with electrochemical systems to efficiently design and optimize a new class of strain-modulated energy storage materials.

  14. Developing adaptive QM/MM computer simulations for electrochemistry.

    PubMed

    Dohm, Sebastian; Spohr, Eckhard; Korth, Martin

    2017-01-05

    We report the development of adaptive QM/MM computer simulations for electrochemistry, providing public access to all sources via the free and open source software development model. We present a modular workflow-based MD simulation code as a platform for algorithms for partitioning space into different regions, which can be treated at different levels of theory on a per-timestep basis. Currently implemented algorithms focus on targeting molecules and their solvation layers relevant to electrochemistry. Instead of using built-in forcefields and quantum mechanical methods, the code features a universal interface, which allows for extension to a range of external forcefield programs and programs for quantum mechanical calculations, thus enabling the user to readily implement interfaces to those programs. The purpose of this article is to describe our codes and illustrate its usage. © 2016 Wiley Periodicals, Inc.

  15. Lithium-sulfur batteries: electrochemistry, materials, and prospects.

    PubMed

    Yin, Ya-Xia; Xin, Sen; Guo, Yu-Guo; Wan, Li-Jun

    2013-12-09

    With the increasing demand for efficient and economic energy storage, Li-S batteries have become attractive candidates for the next-generation high-energy rechargeable Li batteries because of their high theoretical energy density and cost effectiveness. Starting from a brief history of Li-S batteries, this Review introduces the electrochemistry of Li-S batteries, and discusses issues resulting from the electrochemistry, such as the electroactivity and the polysulfide dissolution. To address these critical issues, recent advances in Li-S batteries are summarized, including the S cathode, Li anode, electrolyte, and new designs of Li-S batteries with a metallic Li-free anode. Constructing S molecules confined in the conductive microporous carbon materials to improve the cyclability of Li-S batteries serves as a prospective strategy for the industry in the future. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 2010 ELECTROCHEMISTRY GRC, JANUARY 9-15, 2010, VENTURA, CA

    SciTech Connect

    Stephen Creager

    2010-12-31

    Electrochemical science plays a crucial role in many important technologies and is intimately involved in many natural phenomena. Several new Gordon Research Conferences have appeared recently that are dedicated to electrochemical technologies, however electrochemistry as a discipline continues to thrive and provide the underpinnings of these technologies. The 2010 Electrochemistry GRC will focus on a wide range of fundamental electrochemical phenomena and materials and on their application in areas involving energy storage, information storage, chemical analysis, and motion actuation. The meeting will include sessions dedicated to the following specific topics: electrochemical energy storage (e.g. batteries; at least two sessions); electrochemical motion actuation (e.g. electrokinesis); electrocatalysis; electrochemistry in digital information storage; and bioelectrochemistry (including bioanalysis). An Open Session devoted to highlighting the activities of {approx}10 young investigators and non-North American visitors via brief 10-minute talks, and two open poster sessions highlighting the contributions of approximately 60 conference participants including graduate students, will be held. Altogether the conference is expected to include approximately 90 presentations. As has been the case in the recent past, the meeting will bring together participants from academia, national labs, and the private sector, including senior and junior-level scientists, postdoctoral scientists, and graduate students for informal interactions and exchange of ideas. An affiliated Gordon-Kenan Research Seminar (GRS) will also be held with the conference. Special efforts will be made to invite participation from members of underrepresented groups.

  17. Development of an Electrochemistry Teaching Sequence using a Phenomenographic Approach

    NASA Astrophysics Data System (ADS)

    Rodriguez-Velazquez, Sorangel

    Electrochemistry is the area of chemistry that studies electron transfer reactions across an interface. Chemistry education researchers have acknowledged that difficulties in electrochemistry instruction arise due to the level of abstraction of the topic, lack of adequate explanations and representations found in textbooks, and a quantitative emphasis in the application of concepts. Studies have identified conceptions (also referred to as misconceptions, alternative conceptions, etc.) about the electrochemical process that transcends academic and preparation levels (e.g., students and instructors) as well as cultural and educational settings. Furthermore, conceptual understanding of the electrochemical process requires comprehension of concepts usually studied in physics such as electric current, resistance and potential and often neglected in introductory chemistry courses. The lack of understanding of physical concepts leads to students. conceptions with regards to the relation between the concepts of redox reactions and electric circuits. The need for instructional materials to promote conceptual understanding of the electrochemical process motivated the development of the electrochemistry teaching sequence presented in this dissertation. Teaching sequences are educational tools that aim to bridge the gap between student conceptions and the scientific acceptable conceptions that instructors expect students to learn. This teaching sequence explicitly addresses known conceptions in electrochemistry and departs from traditional instruction in electrochemistry to reinforce students. previous knowledge in thermodynamics providing the foundation for the explicit relation of redox reactions and electric circuits during electrochemistry instruction. The scientific foundations of the electrochemical process are explained based on the Gibbs free energy (G) involved rather than on the standard redox potential values (E° ox/red) of redox half-reactions. Representations of

  18. Solvents' Critical Role in Nonaqueous Lithium-Oxygen Battery Electrochemistry.

    PubMed

    McCloskey, B D; Bethune, D S; Shelby, R M; Girishkumar, G; Luntz, A C

    2011-05-19

    Among the many important challenges facing the development of Li-air batteries, understanding the electrolyte's role in producing the appropriate reversible electrochemistry (i.e., 2Li(+) + O2 + 2e(-) ↔ Li2O2) is critical. Quantitative differential electrochemical mass spectrometry (DEMS), coupled with isotopic labeling of oxygen gas, was used to study Li-O2 electrochemistry in various solvents, including carbonates (typical Li ion battery solvents) and dimethoxyethane (DME). In conjunction with the gas-phase DEMS analysis, electrodeposits formed during discharge on Li-O2 cell cathodes were characterized using ex situ analytical techniques, such as X-ray diffraction and Raman spectroscopy. Carbonate-based solvents were found to irreversibly decompose upon cell discharge. DME-based cells, however, produced mainly lithium peroxide on discharge. Upon cell charge, the lithium peroxide both decomposed to evolve oxygen and oxidized DME at high potentials. Our results lead to two conclusions; (1) coulometry has to be coupled with quantitative gas consumption and evolution data to properly characterize the rechargeability of Li-air batteries, and (2) chemical and electrochemical electrolyte stability in the presence of lithium peroxide and its intermediates is essential to produce a truly reversible Li-O2 electrochemistry.

  19. Redox-capacitor to connect electrochemistry to redox-biology.

    PubMed

    Kim, Eunkyoung; Leverage, W Taylor; Liu, Yi; White, Ian M; Bentley, William E; Payne, Gregory F

    2014-01-07

    It is well-established that redox-reactions are integral to biology for energy harvesting (oxidative phosphorylation), immune defense (oxidative burst) and drug metabolism (phase I reactions), yet there is emerging evidence that redox may play broader roles in biology (e.g., redox signaling). A critical challenge is the need for tools that can probe biologically-relevant redox interactions simply, rapidly and without the need for a comprehensive suite of analytical methods. We propose that electrochemistry may provide such a tool. In this tutorial review, we describe recent studies with a redox-capacitor film that can serve as a bio-electrode interface that can accept, store and donate electrons from mediators commonly used in electrochemistry and also in biology. Specifically, we (i) describe the fabrication of this redox-capacitor from catechols and the polysaccharide chitosan, (ii) discuss the mechanistic basis for electron exchange, (iii) illustrate the properties of this redox-capacitor and its capabilities for promoting redox-communication between biology and electrodes, and (iv) suggest the potential for enlisting signal processing strategies to "extract" redox information. We believe these initial studies indicate broad possibilities for enlisting electrochemistry and signal processing to acquire "systems level" redox information from biology.

  20. Semiconductor electrochemistry of coal pyrite. Technical progress report, January--March 1992

    SciTech Connect

    Osseo-Asare, K.

    1992-05-01

    This project seeks to advance the fundamental understanding of the physicochemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. A novel approach to the study of pyrite aqueous electrochemistry is proposed, based on the use of both synthetic and natural (i.e. coal-derived) pyrite specimens, the utilization of pyrite both in the form of micro (i.e. colloidal and subcolloidal) and macro (i.e. rotating ring disk)-electrodes, and the application of in-situ direct electroanalytical and spectroelectrochemical characterization techniques. Central to this research is the recognition that pyrite is a semiconductor material. (Photo)electrochemical experiments will be conducted to unravel the mechanisms of anodic and cathodic processes such as those associated with pyrite decomposition and the reduction of oxidants such as molecular oxygen and the ferric ion.

  1. Advanced Electrochemistry of Individual Metal Clusters Electrodeposited Atom by Atom to Nanometer by Nanometer.

    PubMed

    Kim, Jiyeon; Dick, Jeffrey E; Bard, Allen J

    2016-11-15

    Metal clusters are very important as building blocks for nanoparticles (NPs) for electrocatalysis and electroanalysis in both fundamental and applied electrochemistry. Attention has been given to understanding of traditional nucleation and growth of metal clusters and to their catalytic activities for various electrochemical applications in energy harvesting as well as analytical sensing. Importantly, understanding the properties of these clusters, primarily the relationship between catalysis and morphology, is required to optimize catalytic function. This has been difficult due to the heterogeneities in the size, shape, and surface properties. Thus, methods that address these issues are necessary to begin understanding the reactivity of individual catalytic centers as opposed to ensemble measurements, where the effect of size and morphology on the catalysis is averaged out in the measurement. This Account introduces our advanced electrochemical approaches to focus on each isolated metal cluster, where we electrochemically fabricated clusters or NPs atom by atom to nanometer by nanometer and explored their electrochemistry for their kinetic and catalytic behavior. Such approaches expand the dimensions of analysis, to include the electrochemistry of (1) a discrete atomic cluster, (2) solely a single NP, or (3) individual NPs in the ensemble sample. Specifically, we studied the electrocatalysis of atomic metal clusters as a nascent electrocatalyst via direct electrodeposition on carbon ultramicroelectrode (C UME) in a femtomolar metal ion precursor. In addition, we developed tunneling ultramicroelectrodes (TUMEs) to study electron transfer (ET) kinetics of a redox probe at a single metal NP electrodeposited on this TUME. Owing to the small dimension of a NP as an active area of a TUME, extremely high mass transfer conditions yielded a remarkably high standard ET rate constant, k(0), of 36 cm/s for outer-sphere ET reaction. Most recently, we advanced nanoscale

  2. A Conceptual Change Teaching Strategy To Facilitate High School Students' Understanding of Electrochemistry.

    ERIC Educational Resources Information Center

    Niaz, Mansoor; Chacon, Eleazar

    2003-01-01

    Describes a study that used a teaching strategy based on two teaching experiments which could facilitate students' conceptual understanding of electrochemistry. Involves two sections (n=29 and n=28) of 10th grade high school students in Venezuela. Concludes that the teaching experiments facilitated student understanding of electrochemistry.…

  3. A Conceptual Change Teaching Strategy To Facilitate High School Students' Understanding of Electrochemistry.

    ERIC Educational Resources Information Center

    Niaz, Mansoor; Chacon, Eleazar

    2003-01-01

    Describes a study that used a teaching strategy based on two teaching experiments which could facilitate students' conceptual understanding of electrochemistry. Involves two sections (n=29 and n=28) of 10th grade high school students in Venezuela. Concludes that the teaching experiments facilitated student understanding of electrochemistry.…

  4. Mechanistic studies of pyridinium electrochemistry: alternative chemical pathways in the presence of CO2.

    PubMed

    Peroff, A G; Weitz, E; Van Duyne, R P

    2016-01-21

    Protonated heterocyclic amines, such as pyridinium, have been utilized as catalysts in the electrocatalytic reduction of carbon dioxide. While these represent a new and exciting class of electrocatalysts, the details of the mechanism and faradaic processes occurring in solution are unclear. We report a series of cyclic voltammetry experiments involving Pt, Ag, Au, and Cu electrodes, under both aqueous and nonaqueous conditions, directed towards gaining an improved mechanistic understanding of pyridinium electrochemistry. Surface-enhanced Raman (SER) spectroelectrochemistry was also performed on Cu film-over-nanosphere electrodes in order to identify adsorbed species. It was found that the reduction potential of pyridinium (-0.58 V vs. SCE) and its electrochemical reversibility are unique features of platinum electrodes. In contrast, the reduction potentials on Ag, Au, and Cu electrodes are ∼400 mV more negative than Pt in both the presence and the absence of CO2. SER spectroelectrochemistry of pyridinium solutions shows no evidence for a pyridinium radical or a pyridinium ion. Increased cathodic current in the presence of CO2 is only detected at scan rates less than 10 mV s(-1) in aqueous solutions. The addition of CO2 resulted in a shift in the potential for the hydrogen evolution reaction. Pyridinium electrochemistry was observed under nonaqueous conditions; however no increase in cathodic current was observed when CO2 was added to the solution. Based on this set of results it is concluded that the reduction potential of pyridinium is surface dependent, CO2 acts as a pseudo-reserve of H(+), and pyridinium and CO2 create an alternative mechanism for hydrogen evolution.

  5. An innovative spectroelectrochemical reflection cell for rapid protein electrochemistry and ultraviolet/visible/infrared spectroscopy.

    PubMed

    Bernad, Sophie; Mäntele, Werner

    2006-04-15

    A novel electrochemical reflection cell combining electrochemical techniques and spectroscopy which uses a solid gold working electrode as an optical mirror is described. This cell can be used at path lengths as low as a few micrometers and thus is suitable for ultraviolet/visible (UV/Vis) and infrared spectroscopy even for aqueous solutions and suspensions. The cell was designed for small sample volumes of only a few microliters, thus reducing the effort for sample preparation. Due to the short path length of some micrometers, the entire volume is within the Nernst diffusion layer, hence resulting in fast equilibration. Evaluation of the technique is described with direct electrochemistry of horse heart cytochrome c at the gold electrode modified with 4,4'-dithiodipyridine. Cyclic voltammograms indicate rapid and reversible electrochemistry with the correct midpoint potential (52 mV vs Ag/AgCl/3 M KCl). Chronoamperometry and coulometry confirm rapid and complete oxidation and reduction; the cell volume can be entirely fully reduced within less than 10-20 s. Spectroscopy in the UV/Vis region, with potentials at the working electrode stepped between -390 and 390 mV, show perfect titration of the cytochrome c heme bands. A Nernst fit of the alpha band absorption, with redox potential Em and number of electrons n left as parameters, yields a midpoint potential of 49 mV and n=0.9. The potential of this cell in the investigation of biological electron transfer reactions and in the study of bioenergetic systems is discussed.

  6. Microbial Electrochemistry and its Application to Energy and Environmental Issues

    NASA Astrophysics Data System (ADS)

    Hastings, Jason Thomas

    Microbial electrochemistry forms the basis of a wide range of topics from microbial fuel cells to fermentation of carbon food sources. The ability to harness microbial electron transfer processes can lead to a greener and cleaner future. This study focuses on microbial electron transfer for liquid fuel production, novel electrode materials, subsurface environments and removal of unwanted byproducts. In the first chapter, exocellular electron transfer through direct contact utilizing passive electrodes for the enhancement of bio-fuel production was tested. Through the application of microbial growth in a 2-cell apparatus on an electrode surface ethanol production was enhanced by 22.7% over traditional fermentation. Ethanol production efficiencies of close to 95% were achieved in a fraction of the time required by traditional fermentation. Also, in this chapter, the effect of exogenous electron shuttles, electrode material selection and resistance was investigated. Power generation was observed using the 2-cell passive electrode system. An encapsulation method, which would also utilize exocellular transfer of electrons through direct contact, was hypothesized for the suspension of viable cells in a conductive polymer substrate. This conductive polymer substrate could have applications in bio-fuel production. Carbon black was added to a polymer solution to test electrospun polymer conductivity and cell viability. Polymer morphology and cell viability were imaged using electron and optical microscopy. Through proper encapsulation, higher fuel production efficiencies would be achievable. Electron transfer through endogenous exocellular protein shuttles was observed in this study. Secretion of a soluble redox active exocellular protein by Clostridium sp. have been shown utilizing a 2-cell apparatus. Cyclic voltammetry and gel electrophoresis were used to show the presence of the protein. The exocellular protein is capable of reducing ferrous iron in a

  7. Graphene Quantum Dots Electrochemistry and Sensitive Electrocatalytic Glucose Sensor Development.

    PubMed

    Gupta, Sanju; Smith, Tyler; Banaszak, Alexander; Boeckl, John

    2017-09-29

    Graphene quantum dots (GQDs), derived from functionalized graphene precursors are graphene sheets a few nanometers in the lateral dimension having a several-layer thickness. They are zero-dimensional materials with quantum confinement and edge site effects. Intense research interest in GQDs is attributed to their unique physicochemical phenomena arising from the sp²-bonded carbon nanocore surrounded with edged plane functional moieties. In this work, GQDs are synthesized by both solvothermal and hydrothermal techniques, with the optimal size of 5 nm determined using high-resolution transmission electron microscopy, with additional UV-Vis absorption and fluorescence spectroscopy, revealing electronic band signatures in the blue-violet region. Their potential in fundamental (direct electron transfer) and applied (enzyme-based glucose biosensor) electrochemistry has been practically realized. Glucose oxidase (GOx) was immobilized on glassy carbon (GC) electrodes modified with GQDs and functionalized graphene (graphene oxide and reduced form). The cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy are used for characterizing the direct electron transfer kinetics and electrocatalytical biosensing. The well-defined quasi-reversible redox peaks were observed under various electrochemical environment and conditions (pH, concentration, scan rate) to determine the diffusion coefficient (D) and first-order electron transfer rate (kET). The cyclic voltammetry curves showed homogeneous ion transport behavior for GQD and other graphene-based samples with D ranging between 8.45 × 10(-9) m² s(-1) and 3 × 10(-8) m² s(-1) following the order of GO < rGO < GQD < GQD (with FcMeOH as redox probe) < GOx/rGO < GOx/GO < HRP/GQDs < GOx/GQDs. The developed GOx-GQDs biosensor responds efficiently and linearly to the presence of glucose over concentrations ranging between 10 μM and 3 mM with a limit of detection of 1.35 μM and sensitivity of

  8. Graphene electrochemistry: fundamental concepts through to prominent applications.

    PubMed

    Brownson, Dale A C; Kampouris, Dimitrios K; Banks, Craig E

    2012-11-07

    The use of graphene, a one atom thick individual planar carbon layer, has exploded in a plethora of scientific disciplines since it was reported to possess a range of unique and exclusive properties. Despite graphene being explored theoretically since the 1940s and known to exist since the 1960s, the recent burst of interest from a large proportion of scientists globally can be correlated with work by Geim and Novoselov in 2004/5, who reported the so-called "scotch tape method" for the production of graphene in addition to identifying its unique electronic properties which has escalated into graphene being reported to be superior in a superfluity of areas. Consequently, many are involved in the pursuit of producing new methodologies to fabricate pristine graphene on an industrial scale in order to meet the current world-wide appetite for graphene. One area which receives considerable interest is the field of electrochemistry, where graphene has been reported to be beneficial in various applications ranging from sensing through to energy storage and generation and carbon based molecular electronics. Electrochemistry is an interfacial technique which is dominated by processes that occur at the solid-liquid interface and thus with the correct understanding can be beneficially utilised to characterise the surface under investigation. In this tutorial review we overview fundamental concepts of Graphene Electrochemistry, making electrochemical characterisation accessible to those who are working on new methodologies to fabricate graphene, bridging the gap between materials scientists and electrochemists and also assisting those exploring graphene in electrochemical areas, or that wish to start to. An overview of the recent understanding of graphene modified electrodes is also provided, highlighting prominent applications reported in the current literature.

  9. Synthesis, Electrochemistry, and Photophysics of Aza-BODIPY Porphyrin Dyes.

    PubMed

    Pascal, Simon; Bucher, Léo; Desbois, Nicolas; Bucher, Christophe; Andraud, Chantal; Gros, Claude P

    2016-03-24

    The synthesis of dyad and triad aza-BODIPY-porphyrin systems in two steps starting from an aryl-substituted aza-BODIPY chromophore is described. The properties of the resulting aza-BODIPY-porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Impact Electrochemistry of Layered Transition Metal Dichalcogenides.

    PubMed

    Lim, Chee Shan; Tan, Shu Min; Sofer, Zdeněk; Pumera, Martin

    2015-08-25

    Layered transition metal dichalcogenides (TMDs) exhibit paramount importance in the electrocatalysis of the hydrogen evolution reaction. It is crucial to determine the size of the electrocatalytic particles as well as to establish their electrocatalytic activity, which occurs at the edges of these particles. Here, we show that individual TMD (MoS2, MoSe2, WS2, or WSe2; in general MX2) nanoparticles impacting an electrode surface provide well-defined current "spikes" in both the cathodic and anodic regions. These spikes originate from direct oxidation of the nanoparticles (from M(4+) to M(6+)) at the anodic region and from the electrocatalytic currents generated upon hydrogen evolution in the cathodic region. The positive correlation between the frequency of the impacts and the concentration of TMD nanoparticles is also demonstrated here, enabling determination of the concentration of TMD nanoparticles in colloidal form. In addition, the size of individual TMD nanoparticles can be evaluated using the charge passed during every spike. The capability of detecting both the "indirect" catalytic effect of an impacting TMD nanoparticle as well as "direct" oxidation indicates that the frequency of impacts in both the "indirect" and "direct" scenarios are comparable. This suggests that all TMD nanoparticles, which are electrochemically oxidizable (thus capable of donating electrons to electrodes), are also capable of catalyzing the hydrogen reduction reaction.

  11. Nanoscale methods for single-molecule electrochemistry.

    PubMed

    Mathwig, Klaus; Aartsma, Thijs J; Canters, Gerard W; Lemay, Serge G

    2014-01-01

    The development of experiments capable of probing individual molecules has led to major breakthroughs in fields ranging from molecular electronics to biophysics, allowing direct tests of knowledge derived from macroscopic measurements and enabling new assays that probe population heterogeneities and internal molecular dynamics. Although still somewhat in their infancy, such methods are also being developed for probing molecular systems in solution using electrochemical transduction mechanisms. Here we outline the present status of this emerging field, concentrating in particular on optical methods, metal-molecule-metal junctions, and electrochemical nanofluidic devices.

  12. Facile synthesis of cuprous oxide nanoparticles by plasma electrochemistry

    NASA Astrophysics Data System (ADS)

    Chen, Qiang; Liu, Jiandi; Yue, Guanghui

    2015-09-01

    Cuprous oxide nanoparticles were synthesized by plasma electrochemistry. In the plasma electrochemistry system, plasma was contacted with the solution as one electrode and a Cu plate immersed in the solutions as the counter electrode. NaCl solution was used as the basic electrolyte and glucose was added as a reaction mediator and/or a reducing agent. The plasma created many reducing and oxidizing species which can react with the Cu ions released from the Cu plate in the solution. Cu2O nanoparticles with an average diameter of about 30 nm were formed under the competition of reducing and oxidizing reactions. The results show that the concentration of added glucose strongly affects the properties of the products. Corresponding to high, medium and low concentrations of glucose, the products were, respectively, nanoparticles of amorphous Cu2O, polycrystalline Cu2O, and a mixture of polycrystalline Cu2O and Cu2Cl(OH)3. This work was partially supported by the National Natural Science Foundation of China (Grant No: 11405144) and the Fundamental Research Funds for the Central Universities (Grant No: 20720150022).

  13. Using a Teaching Model to Correct Known Misconceptions in Electrochemistry

    NASA Astrophysics Data System (ADS)

    Huddle, P. A.; White, Margaret Dawn; Rogers, Fiona

    2000-01-01

    Several misconceptions in electrochemistry have been identified in the literature. No concrete suggestions for remediation of these misconceptions have been proposed. A concrete teaching model for electrochemistry is presented here. It addresses many common student misconceptions about current flow by demonstrating what is occurring at the microscopic level in an electrochemical cell. Both the scope and limitations of the model are discussed. The model was piloted on grade 12 school pupils before being tested on university students. A questionnaire consisting of eight items was administered to three classes of chemistry I students at the University of the Witwatersrand prior to their seeing the model. The dangers of multiple choice questions as a means of determining student understanding of chemical concepts were exposed. The model was then demonstrated to two of the classes. Statistical analysis using a 1-tailed Z-test showed that the use of the model led to significant improvements (0.000 < p < 0.002) in the post-test scores of the experimental groups relative to the control group to indicate current flow in the electrolytes and salt bridge at the microscopic level.

  14. Micro scale electrochemistry: Application to fuel cells

    NASA Astrophysics Data System (ADS)

    O'Hayre, Ryan

    Fuel cells offer the tantalizing promise of cleaner electricity with less environmental impact than traditional energy conversion technologies. This is because fuel cells are direct electrochemical energy conversion devices. Currently, fuel cell technology's greatest disadvantage is cost. Today (2004), fuel cell technology is only economically competitive onboard the Space Shuttle. Recently, fuel cell costs have declined due to technological successes from nanostructured materials. In spite of this success, greater cost reductions and other challenges remain. Furthermore, we are far from possessing a solid scientific understanding of what really goes on at the nano-scale inside fuel cells. Such understanding is critical for further progress. This thesis pioneers several novel electrochemical techniques to study fuel cells at sub-micron length scales. A first technique employs platinum microelectrodes to examine the "triple phase boundary" (TPB) properties of polymer electrolyte fuel cells. By constructing geometrically simple, well-defined electrocatalyst structures of various sizes, a relationship between electrocatalyst geometry and electrochemical behavior is clearly delineated. This study provides perhaps the most direct experimental validation to date of the TPB theory. Extending characterization abilities to the nano-scale, a second technique, called atomic force microscopy (AFM) impedance imaging, is developed. AFM impedance imaging allows highly localized measurements of electrochemical properties to be acquired across sample surfaces. The technique is used to qualitatively visualize sub-micron variations in the electrochemical properties of Nafion (fuel cell electrolyte) samples. The AFM impedance technique is further refined by development of a quantitative measurement methodology. This methodology is validated by AFM impedance studies of the oxygen reduction reaction (ORR) at nano-scale Platinum/Nafion contacts. Use of the quantitative AFM impedance

  15. Eigenstress model for electrochemistry of solid surfaces

    PubMed Central

    Ma, Hongxin; Xiong, Xilin; Gao, Panpan; Li, Xi; Yan, Yu; Volinsky, Alex A.; Su, Yanjing

    2016-01-01

    Thermodynamic analysis and molecular dynamics simulations were conducted to systematically study the size-dependent electrochemical response of solids. By combining the generalized Young-Laplace equation with the popular Butler-Volmer formulation, the direct influence of surface stress on solid film electrochemical reactions was isolated. A series of thermodynamic formulas were developed to describe the size-dependent electrochemical properties of the solid surface. These formulas include intrinsic surface elastic parameters, such as surface eigenstress and surface elastic modulus. Metallic films of Au, Pt, Ni, Cu and Fe were studied as examples. The anodic current density of the metal film increased, while the equilibrium potential decreased with increasing solid film thickness. PMID:27256492

  16. Modulation of Wetting Gradients by Tuning the Interplay between Surface Structuration and Anisotropic Molecular Layers with Bipolar Electrochemistry.

    PubMed

    Bouffier, Laurent; Reculusa, Stéphane; Ravaine, Valérie; Kuhn, Alexander

    2017-10-06

    A new simple and versatile method for the preparation of surface-wetting gradients is proposed. It is based on the combination of electrode surface structuration introduced by a sacrificial template approach and the formation of a tunable molecular gradient by bipolar electrochemistry. The gradient involves the formation of a self-assembled monolayer on a gold surface by selecting an appropriate thiol molecule and subsequent reductive desorption by means of bipolar electrochemistry. Under these conditions, completion of the reductive desorption process evolves along the bipolar surface with a maximum strength localized at the cathodic edge and a decreasing driving force towards the middle of the surface. The remaining quantity of surface-immobilized thiol, therefore, varies as a function of the axial position, resulting in the formation of a molecular gradient. The surface of the bipolar electrode is characterized at each step of the modification by recording heterogeneous electron transfer. Also, the evolution of static contact angles measured with a water droplet deposited on the surface directly reveals the presence of the wetting gradient, which can be modulated by changing the properties of the thiol. This is exemplified with a long, hydrophobic alkane-thiol and a short, hydrophilic mercaptan. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Electroanalytical Evaluation of Nanoparticles by Nano-impact Electrochemistry

    NASA Astrophysics Data System (ADS)

    Karimi, Anahita

    Applications of engineered nanoparticles in electronics, catalysis, solid oxide fuel cells, medicine and sensing continue to increase. Traditionally, nanoparticle systems are characterized by spectroscopic and microscopic techniques. These methods are cumbersome and expensive, which limit their routine use for screening purposes. Electrochemistry is a powerful, yet underutilized tool, for the detection and classification of nanoparticles. The first part of this dissertation investigates a recently developed electrochemical method -- nanoparticle collision electrochemistry -- for detection and characterization of nanoparticles. Three independent projects have been described to evaluate the use of this technique for characterizing nanoparticle based systems including: conjugation with biomolecules, interaction with environmental contaminants and fundamental investigation of conformational changes of nanoparticle capping ligands. The thesis reports the first use of nano-impact electrochemistry to quantitatively investigate bioconjugation and biomolecular recognition at conductive nanoparticles. Furthermore, we also demonstrate the potential of this method as a single step, reagentless and label-free technique for the ultra-sensitive detection of biomolecular targets. A fundamental study of biorecognition is important for the development of therapeutics and molecular diagnosis probes in the biomedical, biosensing and biotechnology fields. The second project describes the use of this method as a screening tool of particle reactivity. We study the interaction and adsorption of a toxic environmental metalloid (Arsenic) with metal oxide nanoparticles to extract mechanistic, speciation and loading information. We discuss the potential of this approach to complement or replace costly characterization techniques and enable routine study of nanoparticles and their reactivity. In the third project, we use the nano-impact method to study the pH-dependent conformational changes

  18. Solid-state electrochemistry on the nanometer and atomic scales: the scanning probe microscopy approach

    DOE PAGES

    Strelcov, Evgheni; Yang, Sang Mo; Jesse, Stephen; ...

    2016-04-21

    Energy technologies of the 21st century require an understanding and precise control over ion transport and electrochemistry at all length scales – from single atoms to macroscopic devices. Our short review provides a summary of recent studies dedicated to methods of advanced scanning probe microscopy for probing electrochemical transformations in solids at the meso-, nano- and atomic scales. In this discussion we present the advantages and limitations of several techniques and a wealth of examples highlighting peculiarities of nanoscale electrochemistry.

  19. Solid-state electrochemistry on the nanometer and atomic scales: the scanning probe microscopy approach

    SciTech Connect

    Strelcov, Evgheni; Yang, Sang Mo; Jesse, Stephen; Balke, Nina; Vasudevan, Rama K.; Kalinin, Sergei V.

    2016-04-21

    Energy technologies of the 21st century require an understanding and precise control over ion transport and electrochemistry at all length scales – from single atoms to macroscopic devices. Our short review provides a summary of recent studies dedicated to methods of advanced scanning probe microscopy for probing electrochemical transformations in solids at the meso-, nano- and atomic scales. In this discussion we present the advantages and limitations of several techniques and a wealth of examples highlighting peculiarities of nanoscale electrochemistry.

  20. Solid-state electrochemistry on the nanometer and atomic scales: the scanning probe microscopy approach

    PubMed Central

    Strelcov, Evgheni; Yang, Sang Mo; Jesse, Stephen; Balke, Nina; Vasudevan, Rama K.; Kalinin, Sergei V.

    2016-01-01

    Energy technologies of the 21st century require understanding and precise control over ion transport and electrochemistry at all length scales – from single atoms to macroscopic devices. This short review provides a summary of recent works dedicated to methods of advanced scanning probe microscopy for probing electrochemical transformations in solids at the meso-, nano- and atomic scales. Discussion presents advantages and limitations of several techniques and a wealth of examples highlighting peculiarities of nanoscale electrochemistry. PMID:27146961

  1. Individuals achieve more accurate results with meters that are codeless and employ dynamic electrochemistry.

    PubMed

    Rao, Anoop; Wiley, Meg; Iyengar, Sridhar; Nadeau, Dan; Carnevale, Julie

    2010-01-01

    Studies have shown that controlling blood glucose can reduce the onset and progression of the long-term microvascular and neuropathic complications associated with the chronic course of diabetes mellitus. Improved glycemic control can be achieved by frequent testing combined with changes in medication, exercise, and diet. Technological advancements have enabled improvements in analytical accuracy of meters, and this paper explores two such parameters to which that accuracy can be attributed. Four blood glucose monitoring systems (with or without dynamic electrochemistry algorithms, codeless or requiring coding prior to testing) were evaluated and compared with respect to their accuracy. Altogether, 108 blood glucose values were obtained for each system from 54 study participants and compared with the reference values. The analysis depicted in the International Organization for Standardization table format indicates that the devices with dynamic electrochemistry and the codeless feature had the highest proportion of acceptable results overall (System A, 101/103). Results were significant when compared at the 10% bias level with meters that were codeless and utilized static electrochemistry (p = .017) or systems that had static electrochemistry but needed coding (p = .008). Analytical performance of these blood glucose meters differed significantly depending on their technologic features. Meters that utilized dynamic electrochemistry and did not require coding were more accurate than meters that used static electrochemistry or required coding. 2010 Diabetes Technology Society.

  2. Individuals Achieve More Accurate Results with Meters That Are Codeless and Employ Dynamic Electrochemistry

    PubMed Central

    Rao, Anoop; Wiley, Meg; Iyengar, Sridhar; Nadeau, Dan; Carnevale, Julie

    2010-01-01

    Background Studies have shown that controlling blood glucose can reduce the onset and progression of the long-term microvascular and neuropathic complications associated with the chronic course of diabetes mellitus. Improved glycemic control can be achieved by frequent testing combined with changes in medication, exercise, and diet. Technological advancements have enabled improvements in analytical accuracy of meters, and this paper explores two such parameters to which that accuracy can be attributed. Methods Four blood glucose monitoring systems (with or without dynamic electrochemistry algorithms, codeless or requiring coding prior to testing) were evaluated and compared with respect to their accuracy. Results Altogether, 108 blood glucose values were obtained for each system from 54 study participants and compared with the reference values. The analysis depicted in the International Organization for Standardization table format indicates that the devices with dynamic electrochemistry and the codeless feature had the highest proportion of acceptable results overall (System A, 101/103). Results were significant when compared at the 10% bias level with meters that were codeless and utilized static electrochemistry (p = .017) or systems that had static electrochemistry but needed coding (p = .008). Conclusions Analytical performance of these blood glucose meters differed significantly depending on their technologic features. Meters that utilized dynamic electrochemistry and did not require coding were more accurate than meters that used static electrochemistry or required coding. PMID:20167178

  3. Application of graphene-copper sulfide nanocomposite modified electrode for electrochemistry and electrocatalysis of hemoglobin.

    PubMed

    Shi, Fan; Zheng, Weizhe; Wang, Wencheng; Hou, Fei; Lei, Bingxin; Sun, Zhenfan; Sun, Wei

    2015-02-15

    In this paper a graphene (GR) and copper sulfide (CuS) nanocomposite was synthesized by hydrothermal method and used for the electrode modification with a N-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) as the substrate electrode. Hemoglobin (Hb) was immobilized on the modified electrode to get a biocompatible sensing platform. UV-vis absorption spectroscopic results confirmed that Hb retained its native secondary structure in the composite. Direct electron transfer of Hb incorporated into the nanocomposite was investigated with a pair of well-defined redox waves appeared on cyclic voltammogram, indicating the realization of direct electrochemistry of Hb on the modified electrode. The results can be ascribed to the presence of GR-CuS nanocomposite on the electrode surface that facilitates the electron transfer rate between the electroactive center of Hb and the electrode. The Hb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid in the concentration range from 3.0 to 64.0 mmol L(-1) with the detection limit of 0.20 mmol L(-1) (3σ). The fabricated biosensor displayed the advantages such as high sensitivity, good reproducibility and long-term stability.

  4. Inorganic-organic hybrid polyoxometalate: Preparation, characterization and electrochemistry properties

    SciTech Connect

    Han Zhangang; Zhao Yulong; Peng Jun . E-mail: jpeng@nenu.edu.cn; Tian Aixiang; Feng Yuhua; Liu Qun

    2005-05-15

    The solid hybrid material (H{sub 3/4}pbpy){sub 4}[PMo{sub 12}O{sub 40}].1.25H{sub 2}O (1) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) has been prepared and characterized. A structural feature of compound 1 is that the polyoxometalate anions exhibit a one-dimensional inorganic double chain-like structure via weak interactions of O...O. The organic moiety exhibits regular packing with offset aromatic-aromatic interactions between the pbpys, leading to a compact supramolecular framework structure to accommodate the inorganic chains. Compound 1 was employed to fabricate the three-dimensional bulk-modified carbon paste electrode (1-CPE) to research on its electrochemistry properties. The results indicate that 1 retained Keggin molybdate anion electrocatalytic activities toward the reduction of chlorate, hydrogen peroxide and nitrite.

  5. Facile synthesis of cuprous oxide nanoparticles by plasma electrochemistry

    NASA Astrophysics Data System (ADS)

    Liu, Jiandi; Chen, Qiang; Li, Junshuai; Xiong, Qing; Yue, Guanghui; Zhang, Xianhui; Yang, Size; Huo Liu, Qing

    2016-07-01

    We report on a simple plasma electrochemistry method for synthesizing cuprous oxide (Cu2O) nanoparticles in the presence of glucose. In this system, Ar plasma in contact with a NaCl solution was used as one electrode, and a Cu plate was immersed in the solution as the counter electrode. The plasma-solution interaction produced many reducing and oxidizing species which can react with the Cu ions released from the Cu electrode. Cu2O nanoparticles, with an average diameter of 22 +/- 6 nm, were formed under the competition of reducing and oxidizing reactions in the solution. The results show that the glucose added in the electrolyte strongly influences the properties of the products. Corresponding to high, medium, and low concentrations of glucose, the products were nanoparticles from amorphous Cu2O, polycrystalline Cu2O, and a mixture of polycrystalline Cu2O and Cu2Cl(OH)3, respectively.

  6. Electrochemistry of Silicon: Instrumentation, Science, Materials and Applications

    NASA Astrophysics Data System (ADS)

    Lehmann, Volker

    2002-04-01

    Silicon has been and will most probably continue to be the dominant material in semiconductor technology. Although the defect-free silicon single crystal is one of the best understood systems in materails science, its electrochemistry to many people is still a kind of "alchemy". This view is partly due to the interdisciplinary aspects of the topic: Physics meets chemistry at the silicon-electrolyte interface. This book gives a comprehensive overview of this important aspect of silicon technology as well as examples of applications ranging from photonic crystals to biochips. It will serve materials scientists as well as engineers involved in silicon technology as a quick reference with its more than 150 technical tables and diagrams and ca. 1000 references cited for easy access of the original literature.

  7. Single Pt nanowire electrode: preparation, electrochemistry, and electrocatalysis.

    PubMed

    Li, Yongxin; Wu, Qingqing; Jiao, Shoufeng; Xu, Chaodi; Wang, Lun

    2013-04-16

    A single Pt nanowire electrode (SPNE) was fabricated through HF etching process from Pt disk nanoelectrode and an underpotential deposition (UPD) redox replacement technique. The electrochemical experiments showed that SPNE had steady-state electrochemical responses at redox species solution and the mass transfer rates were affected by the lengths and radii of SPNEs. The prepared SPNEs were utilized to examine the oxygen-reduction reaction in a KOH solution to explore the feasibility of electrocatalytic activity of single Pt nanowire and the results showed that the electrocatalytic activity of SPNE was dependent on the surface position of single Pt nanowire: the tip end position is more active than the sidewall position. Meanwhile, the electrocatalytic activity of SPNE was related to the radius of nanowire. These observations are not only important to understand the structure-function relationship in single nanowire level but have significant implications for the synthesis and selection of novel catalysts with high efficiency used in electrochemistry, energy, bioanalysis, etc.

  8. Electrochemistry at Edge of Single Graphene Layer in a Nanopore

    PubMed Central

    Banerjee, Shouvik; Shim, Jiwook; Rivera, Jose; Jin, Xiaozhong; Estrada, David; Solovyeva, Vita; You, Xiuque; Pak, James; Pop, Eric; Aluru, Narayana; Bashir, Rashid

    2013-01-01

    We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and Al2O3 dielectric layers. Nanopores, with diameters ranging from 5 to 20 nm, are formed by an electron beam sculpting process on the stacked layers. This leads to unique edge structure which, along with the atomically thin nature of the embedded graphene electrode, demonstrates electrochemical current densities as high as 1.2 × 104 A/cm2. The graphene edge embedded structure offers a unique capability to study the electrochemical exchange at an individual graphene edge, isolated from the basal plane electrochemical activity. We also report ionic current modulation in the nanopore by biasing the embedded graphene terminal with respect to the electrodes in the fluid. The high electrochemical specific current density for a graphene nanopore-based device can have many applications in sensitive chemical and biological sensing, and energy storage devices. PMID:23249127

  9. Oxygen electrochemistry as a cornerstone for sustainable energy conversion.

    PubMed

    Katsounaros, Ioannis; Cherevko, Serhiy; Zeradjanin, Aleksandar R; Mayrhofer, Karl J J

    2014-01-03

    Electrochemistry will play a vital role in creating sustainable energy solutions in the future, particularly for the conversion and storage of electrical into chemical energy in electrolysis cells, and the reverse conversion and utilization of the stored energy in galvanic cells. The common challenge in both processes is the development of-preferably abundant-nanostructured materials that can catalyze the electrochemical reactions of interest with a high rate over a sufficiently long period of time. An overall understanding of the related processes and mechanisms occurring under the operation conditions is a necessity for the rational design of materials that meet these requirements. A promising strategy to develop such an understanding is the investigation of the impact of material properties on reaction activity/selectivity and on catalyst stability under the conditions of operation, as well as the application of complementary in situ techniques for the investigation of catalyst structure and composition.

  10. Three Redox States of Trypanosoma brucei Alternative Oxidase Identified by Infrared Spectroscopy and Electrochemistry

    PubMed Central

    Maréchal, Amandine; Kido, Yasutoshi; Kita, Kiyoshi; Moore, Anthony L.; Rich, Peter R.

    2009-01-01

    Electrochemistry coupled with Fourier transform infrared (IR) spectroscopy was used to investigate the redox properties of recombinant alternative ubiquinol oxidase from Trypanosoma brucei, the organism responsible for African sleeping sickness. Stepwise reduction of the fully oxidized resting state of recombinant alternative ubiquinol oxidase revealed two distinct IR redox difference spectra. The first of these, signal 1, titrates in the reductive direction as an n = 2 Nernstian component with an apparent midpoint potential of 80 mV at pH 7.0. However, reoxidation of signal 1 in the same potential range under anaerobic conditions did not occur and only began with potentials in excess of 500 mV. Reoxidation by introduction of oxygen was also unsuccessful. Signal 1 contained clear features that can be assigned to protonation of at least one carboxylate group, further perturbations of carboxylic and histidine residues, bound ubiquinone, and a negative band at 1554 cm−1 that might arise from a radical in the fully oxidized protein. A second distinct IR redox difference spectrum, signal 2, appeared more slowly once signal 1 had been reduced. This component could be reoxidized with potentials above 100 mV. In addition, when both signals 1 and 2 were reduced, introduction of oxygen caused rapid oxidation of both components. These data are interpreted in terms of the possible active site structure and mechanism of oxygen reduction to water. PMID:19767647

  11. Electrochemistry of Cytochrome P450 BM3 in Sodium Dodecyl Sulfate Films

    PubMed Central

    Udit, Andrew K.; Hill, Michael G.; Gray, Harry B.

    2008-01-01

    Direct electrochemistry of the cytochrome P450 BM3 heme domain (BM3) was achieved by confining the protein within sodium dodecyl sulfate (SDS) films on the surface of basal-plane graphite (BPG) electrodes. Cyclic voltammetry revealed the heme FeIII/II redox couple at −330 mV (vs. Ag/AgCl, pH 7.4). Up to 10 V/s, the peak current was linear with scan rate, allowing us to treat the system as surface-confined within this regime. The standard heterogeneous rate constant determined at 10 V/s was estimated to be 10 s−1. Voltammograms obtained for the BM3-SDS-BPG system in the presence of dioxygen exhibited catalytic waves at the onset of FeIII reduction. The altered heme reduction potential of the BM3-SDS-graphite system indicates that SDS is likely bound in the enzyme active-site region. Compared to other P450-surfactant systems, we find redox potentials and electron transfer rates that differ by ~ 100 mV and > 10-fold, respectively, indicating that the nature of the surfactant environment has a significant effect on the observed heme redox properties. PMID:17129070

  12. 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

  13. Electronic density functional theory in the grand canonical ensemble, electrochemistry, and the underpotential deposition of Cu/Pt(111)

    NASA Astrophysics Data System (ADS)

    Sundararaman, Ravishankar; Weaver, Kendra; Arias, Tomas

    2012-02-01

    The study of electrochemical systems within electronic density functional theory requires the handling of non-neutral electronic systems in the plane-wave basis in order to accurately describe charged metallic surfaces; this can be accomplished in joint density functional theory by adding an electrolyte with Debye screening ootnotetextK. L. Weaver and T. A. Arias (under preparation). This capability opens up the opportunity to work in the grand canonical ensemble at fixed chemical potential μ for the electrons, which corresponds directly to the experimental setting in electrochemistry. We present efficient techniques for electronic density functional calculations at fixed μ, and demonstrate the improvement in predictive power over conventional neutral calculations using the underpotential deposition of Cu/Pt(111) as an example: for the first time, we calculate absolute voltages for electrochemical processes in excellent agreement with experiment, instead of voltage shifts alone.

  14. Etude du Photochromisme et de la Photorefractivite dans le Poly

    NASA Astrophysics Data System (ADS)

    Ghailane, Fatima

    1995-11-01

    Nous avons etudie la possibilite d'utiliser un materiau organique, le poly(vinylcarbazole) comme milieu de stockage optique de masse en temps reel. Ce materiau dope aux photochromes presente un potentiel non negligeable pour l'holographie de volume en temps reel. Plusiers cycles, Ecriture-Lecture-Effacement, ont ete enregistres dans cette matrice polymerique avec une resolution assez elevee. Une etude a ete menee afin d'obtenir la valeur des parametres comme l'epaisseur du film et l'intensite d'ecriture pour un angle d'enregistrement theta_{ acute ecriture} donne qui permettent d'obtenir les meilleures efficacites diffractionelles tout en preservant ce milieu de tout effet de fatigue ou de degradation. Ce polymere devient photorefractif une fois melange avec un bon accepteur de charge, le trinitrofluorenone et un bon chromophore non-lineaire, le disperse orange 25. Nous avons etudie experimentalement la conductivite en obscurite et la photoconductivite de ce materiau. Des simulations numeriques ont ete realisees en se basant sur le modele de Poole-Frenkel. Nous avons aussi etudie l'implantation de faisceaux d'ions d'oxygene d'energie 200 keV pour inscrire dans le PVCz un guide d'onde plan a profil d'indice. Une etude ESCA complete cette partie afin de savoir les modifications induites par implementation ionique a l'interieur du film polymerique.

  15. Electrochemistry and spectroscopy of energy conversion and polynuclear aromatic materials

    NASA Astrophysics Data System (ADS)

    Nazri, Maryam

    The field of materials chemistry is becoming increasingly important in many technological disciplines, including batteries, fuel cells, hydrogen storage materials, and application of poly-nuclear aromatic compounds in solar cells, color copiers, sensors, and catalysis. This multidisciplinary research work focuses on the development, understanding, and characterization of novel materials for advanced lithium batteries and a unique series of polyaromatic compounds for application in solar cells and color copiers. A general overview of materials and techniques used in this work is presented, including the electrochemistry, spectroscopy, thermal analysis, and x-ray diffraction. A unique electrochemical procedure based on carbon paste microelectrode was applied to study the electrochemistry of novel poly-nuclear aromatic compounds. X-ray diffraction and vibrational spectroscopy are also used to gain further information about their molecular organization in solid-state. Conductivity of a novel electrolyte based on a multi-blend of organic carbonate solvents, has been studied over a wide range of temperatures (-40 to 70°C). An optimized electrolyte for an advanced lithium battery based on ternary solvent blend of linear and cyclic organic carbonates has been developed. The nature of ion-association and ion-solvent interactions in complex electrolytes are studied using infrared spectroscopy. We have found a strong preferred solvation of lithium ion in electrolyte containing multi-blend solvent molecules. The advanced lithium battery uses intercalation compounds with layered structure such as LiCoO2 cathode, and lithiated graphite, (LiC 6), anode. In this work, we have studied the reactivity of Li-C anode materials in contact with organic carbonate-based electrolyte, and have investigated the nature of the decomposition products formed on the electrode surface. A significant reactivity between the LiC6 and organic electrolytes is observed, and is a major safety concern. A

  16. Using the Electrochemistry of the Electrospray Ion Source

    SciTech Connect

    Van Berkel, Gary J; Kertesz, Vilmos

    2007-01-01

    Electrospray mass spectrometry (ES-MS) is one of the more widely used analysis methods in science today, impacting fields as diverse as conventional chemistry to biotechnology and materials science. , Even 20 years after bursting onto the mass spectrometry scene, the underlying processes in ES ionization continue to be better understood exposing new opportunities for the technique. , , , , Such is the case for the improved understanding related to the electrochemical processes inherent to the operation of this ion source, , , which is the topic of this report. Electrospray ionization involves three main steps prior to mass analysis: the generation and charging of the ES droplets; droplet evaporation and the production of gas-phase ions; and secondary processes that modify the gas-phase ions in the atmosphere and the sub-atmospheric pressure sampling regions of the mass spectrometer. Integral to the generation and charging of the ES droplets are electrochemical reactions that occur at the conductive contact/solution interface within or near the ES emitter to maintain the quasi-continuous production of charged droplets and ultimately gas-phase ions. The basic electrochemical phenomena concerning the ES ion source were first brought to wide attention in the mass spectrometry community by Kebarle and co-workers in the early 1990's,8 but the electrochemistry of electrostatic spray devices and possible analytical consequences resulting from this phenomenon were realized and discussed in the literature at least as far back as the mid-1970's. When asked to intercede in a debate on the significance of electrochemistry in the ES ionization (ESI) process, 2002 Nobel Laureate in Chemistry John Fenn noted that to him " the idea that electrochemical reactions might be taking place in an ES ion source was too obvious to mention. That products of such reactions are of vital significance in the overall ESI process was much less obvious. Indeed, it seems fair to say that with few

  17. Etude paleomagnetique des sediments holocenes de la Fosse du Mackenzie, mer de Beaufort

    NASA Astrophysics Data System (ADS)

    Barris, Elissa

    Les etudes paleomagnetiques a haute resolution sont d'importance en magnetostratigraphie et geomagnetisme, particulierement dans l'Arctique en raison de l'inaccessibilite et des faibles vitesses de sedimentation dans plusieurs secteurs. Deux carottes sedimentaires representant l'Holocene recent ont ete recoltees dans la Fosse du Mackenzie, une region avec des vitesses de sedimentation relativement elevees. Une carotte boite et un Calypso square core ont ete preleves a deux sites (690 et 680). Les proprietes physiques et magnetiques et la granulometrie ont ete mesurees, ainsi que les aimantations remanentes naturelle, anhysteretique, isothermale et isothermale saturee (NRM, ARM, IRM et SIRM). L'hysteresis magnetique indique une forte concentration de magnetite de type pseudo-single domain, un porteur ideal de remanence, alors que les mesures de la susceptibilite magnetique suggerent une concentration uniforme. Les valeurs de deviation angulaire maximale (MAD) et du champ median destructif (MDF) indiquent des donnees de direction d'excellente qualite et une coercivite typique de la magnetite, respectivement. Finalement, dans la carotte 690 et la partie intermediaire de la 680, l'inclinaison vane autour des valeurs d'un dipole axial geocentrique (GAD) pour la latitude des sites, renforcant la fiabilite du signal paleomagnetique. Finalement, des proxies de la paleointensite relative ont ete construits pour les carottes 690 et 680 en normalisant la NRM par l'IRM et l'ARM, respectivement. Vingt-et-une coquilles de pelecypodes reparties dans les deux carottes ont ete recoltees pour construire un modele d'âge au radiocarbone a chaque si te, une tâche necessaire pour la mise en contexte d'un enregistrement paleomagnetique, mais souvent difficile dans l'Arctique. En utilisant ces modeles d'âge, les enregistrements paleomagnetiques ont ete compares avec d'autres provenant du bas-Arctique et des moyennes latitudes, soulignant leur potentiel pour des etudes

  18. Synthesis of cryptomelane type α-MnO 2 (K x Mn 8 O 16 ) cathode materials with tunable K + content: the role of tunnel cation concentration on electrochemistry

    SciTech Connect

    Poyraz, Altug S.; Huang, Jianping; Pelliccione, Christopher J.; Tong, Xiao; Cheng, Shaobo; Wu, Lijun; Zhu, Yimei; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.

    2017-01-01

    Here, we synthesized a series of α-MnO2samples with differing K+content but similar physical properties allowing direct study of the role of tunnel K+on the electrochemistry of α-MnO2cathodes.

  19. Electrochemistry combined on-line with electrospray mass spectrometry

    SciTech Connect

    Zhou, F.; Berkel, G.J.V.

    1995-10-15

    In this paper a variety of methods to couple electrochemistry on-line with electrospray mass spectrometry (EC/ES-MS) are presented, and the fundamental and analytical utility of this hybrid technique is illustrated. The major problems encountered in coupling EC and ES-MS are discussed, and means to overcome them are presented. Three types of electrochemical flow cells, viz., a thin-layer electrode flow-by cell, a tubular electrode flow-through cell, and a porous electrode flow-through cell, are discussed in regard to their suitability for this coupling. Methods for coupling each of these electrochemical cells on-line with ES-MS, either floated at or decoupled from the ES high voltage and controlled by a constant current supply, a constant potential supply, or a potentiostat are presented. Three applications are used to illustrate the utility and versatility of the EC/ES-MS combination: (1) the ionization of neutral analytes (i.e., perylene) for detection by ES-MS, (2) the study of the products of electrode reactions (i.e., nickel(II) octaethylporphyrin oxidation products), including relatively short-lived products (i.e., {Beta}-carotene oxidation products), and (3) the enhanced determination of metals (i.e., elemental silver) achieved by coupling anodic stripping voltammetry on-line with ES-MS. 52 refs., 6 figs.

  20. Perspective on Electrospray Ionization and Its Relation to Electrochemistry

    NASA Astrophysics Data System (ADS)

    Pozniak, Boguslaw P.; Cole, Richard B.

    2015-03-01

    The phenomenon of electrospraying of liquids is presented from the perspective of the electrochemistry involved. Basics of current and liquid flow in the capillary and spray tip are discussed, followed by specifics of charging and discharging of the sprayed liquid surface. Fundamental theories and numerical modeling relating electrospray current to solution and spray parameters are described and then compared with our own experimentally obtained data. The method of mapping potentials and currents inside the electrospray capillary by using an inserted electrically-isolated small wire probe electrode is discussed in detail with illustrations from new and published data. Based on these experimentally obtained results, a new mathematical model is derived. The introduced "nonlinear resistor electrospray capillary model" divides the electrospray capillary into small sections, adds their contributions, and then, by transition to infinitely small section thickness, produces analytical formulas that relate current and potential maps to other properties of the electrospraying liquid: primarily conductivity and current density. The presentation of the model is undertaken from an elementary standpoint, and it offers the possibility to obtain quantitative information regarding operating parameters from typical analytical systems subjected to electrospray. The model stresses simplicity and ease of use; examples applying experimental data are shown and some predictions of the model are also presented. The developed nonlinear resistor electrospray capillary model is intended to provide a new quantitative basis for improving the understanding of electrochemical transformations occurring in the electrospray emitter. A supplemental material section gives full derivation of the model and discusses other consequences.

  1. Electrochemistry of moexipril: experimental and computational approach and voltammetric determination.

    PubMed

    Taşdemir, Hüdai I; Kiliç, E

    2014-09-01

    The electrochemistry of moexipril (MOE) was studied by electrochemical methods with theoretical calculations performed at B3LYP/6-31 + G (d)//AM1. Cyclic voltammetric studies were carried out based on a reversible and adsorption-controlled reduction peak at -1.35 V on a hanging mercury drop electrode (HMDE). Concurrently irreversible diffusion-controlled oxidation peak at 1.15 V on glassy carbon electrode (GCE) was also employed. Potential values are according to Ag/AgCI, (3.0 M KCI) and measurements were performed in Britton-Robinson buffer of pH 5.5. Tentative electrode mechanisms were proposed according to experimental results and ab-initio calculations. Square-wave adsorptive stripping voltammetric methods have been developed and validated for quantification of MOE in pharmaceutical preparations. Linear working range was established as 0.03-1.35 microM for HMDE and 0.2-20.0 microM for GCE. Limit of quantification (LOQ) was calculated to be 0.032 and 0.47 microM for HMDE and GCE, respectively. Methods were successfully applied to assay the drug in tablets by calibration and standard addition methods with good recoveries between 97.1% and 106.2% having relative standard deviation less than 10%.

  2. Mechanics and electrochemistry of ionic polymer metal composites

    NASA Astrophysics Data System (ADS)

    Cha, Youngsu; Porfiri, Maurizio

    2014-11-01

    Ionic polymer metal composites (IPMCs) are electroactive materials composed of a hydrated ionomeric membrane that is sandwiched between noble metal electrodes. Here, we propose a modeling framework to study quasi-static large deformations and electrochemistry of IPMCs. Specifically, IPMC kinematics is described in terms of its mechanical deformation, the concentration of mobile counterions neutralizing the ionomer, and the electric potential. The chemoelectromechanical constitutive behavior is obtained from a Helmholtz free energy density, which accounts for mechanical stretching, ion mixing, and electric polarization. The three-dimensional framework is specialized to plane bending of thin IPMCs. Hence, we propose a structural model, where the moment and the charge stored along the IPMC are computed from the solution of a modified Poisson-Nernst-Planck system, in terms of the through-the-thickness coordinate. For small static deformations, we present a semianalytical solution based on the method of matched asymptotic expansions, which is ultimately used to study IPMC sensing and actuation. We demonstrate that the linearity of IPMC actuation in a broad voltage range could be attributed to the interplay of two competing nonlinear phenomena, associated with Maxwell stress and osmotic pressure. In agreement with experimental observations, our model confirms the possibility of tailoring IPMC actuation by varying the counterion size and the concentration of fixed ions. Finally, the model is successful in predicting the significantly different voltage levels displayed by IPMC sensors and actuators, which are associated with remarkable variations in the ion mixing and polarization energies.

  3. Localized dissolution electrochemistry at surface irregularities of pipeline steel

    NASA Astrophysics Data System (ADS)

    Tang, X.; Cheng, Y. F.

    2008-06-01

    The localized electrochemical dissolution behavior at surface irregularities, including scratch, mechanically induced hole and corrosion pit, on pipeline steel was investigated in both near-neutral pH and high pH solutions by scanning vibrating micro-electrode and localized electrochemical impedance spectroscopy measurements. In near-neutral pH solution, the localized dissolution behavior at surface irregularities is dependent of their geometrical depth, which is critical to development of a local electrochemical condition to support the further localized dissolution. Therefore, surface irregularities exceeding a certain depth provide potential sites to initiate stress corrosion cracks in near-neutral pH solution. The strong passivating capability of high pH solution would result in the formation of oxide film over the whole electrode surface to "equalize" the electrochemical activity at irregularities to the intact area. Therefore, the irregularities would not result in localized dissolution electrochemistry. Consequently, localized corrosion and crack initiation are not anticipated to initiate from the geometrical irregularities in high pH solution. However, corrosion pits generating due to passive film breakdown could support the high local dissolution kinetics in high pH solution, providing potential sites for crack initiation. The effects of hydrogen-charging on anodic dissolution at regularities depend on the defect geometry and the solution pH.

  4. Preparation of silver-carbon nanotubes composites with plasma electrochemistry

    NASA Astrophysics Data System (ADS)

    Hoefft, Oliver; Lohmann, Lara; Olschewski, Mark; Endres, Frank

    2016-09-01

    Plasma electrochemistry is a powerful tool to generate free nanoparticles in aqueous solutions and especially in ionic liquids (ILs). Due to their very low vapour pressure, ionic liquids can be employed under vacuum conditions as fluid substrates or solvents. Thus, ionic liquids are well suitable electrolytes for plasma electrochemical processes delivering stable and homogeneous plasmas. We have shown that free copper and germanium nanoparticles can be obtained in ILs by applying a plasma as a mechanically contact-free electrode. Here we present our results using an argon plasma for the electrochemical synthesis of silver on pure and pre-treated multiwall carbon nanotubes (MWCNTs) in 1-ethyl-3-methylimidazolium dicyanamide. For the pre-treatment of the MWCNTS we have used a dielectric barrier discharge plasma (DBD) at atmospheric pressure. For the untreated MWCNTs we have found a formation of free silver nanoparticles between, on and in the vicinity of the carbon nanotubes. In case of the plasma treated MWCNTs a silver-carbon nanotubes composite is formed. Thus, the treatment of the MWCNTs obviously has a great influence on the deposit. Therefore we additionally have investigated the influence of the DBD on the chemical composition of the MWCNTs surface with X-Ray Photoelectron Spectroscopy.

  5. Etude des proprietes electroniques des etats fondamentaux aux facteurs de remplissage entiers dans la bicouche de graphene

    NASA Astrophysics Data System (ADS)

    Lemonde, Marc-Antoine

    Dans ce document, on etudie les proprietes electroniques d'un systeme compose de deux couches de graphene separees par un dielectrique en presence d'un fort champ magnetique perpendiculaire. L'epaisseur du dielectrique est choisie de facon a pouvoir negliger le transfert de charges par effet tunnel. Ce type de systeme est etudie par quelques groupes de recherche dans le principal but de predire et comprendre la formation de condensat de Bose-Einstein d'excitons dont les composants sont des fermions relativistes sans masse [1] [2] [3]. Nous nous interessons a l'effet de l'interaction electron-electron sur les etats fondamentaux de ce systeme et 'a leurs excitations collectives a facteur de remplissage entier. Plus precisement, nous etudions les diagrammes de phase de cette bicouche de graphene sans terme tunnel dans le niveau de Landau n = 0 pour les facteurs de remplissage nu = 1 et nu = 2 dans la limite ou la temperature tend vers zero. Lors de cette etude, nous appuyons les predictions faites par Allan H. MacDonald et Yogesh N. Joglekar a propos de la formation d'un condensat de Bose-Einstein d'excitons pour differentes zones des diagrammes de phase. Nous etudions aussi la relation de dispersion des excitations collectives soutenues par les etats fondamentaux et leur effet sur le systeme. Finalement, nous nous interessons a la conductivite du systeme. Nous demontrons alors les regles de selection pour l'absorption inter-niveaux de Landaux et nous etudions l'effet des modes collectifs sur l'absorption .intrarniveau de Landau, Ce dernier phenomene ressort directement de la forme particuliere du reseau atomique du graphene et nous proposons dans ce document une toute premiere etude de ce concept. Mots-cles : graphene, gaz d'electrons bidimensionnel, effets Hall quantiques, proprietes electroniques, modes collectifs

  6. LIGA-based microsystem manufacturing:the electrochemistry of through-mold depostion and material properties.

    SciTech Connect

    Kelly, James J. (Sandia National Laboratories, Livermore, CA); Goods, Steven Howard (Sandia National Laboratories, Livermore, CA)

    2005-06-01

    The report presented below is to appear in ''Electrochemistry at the Nanoscale'', Patrik Schmuki, Ed. Springer-Verlag, (ca. 2005). The history of the LIGA process, used for fabricating dimensional precise structures for microsystem applications, is briefly reviewed, as are the basic elements of the technology. The principal focus however, is on the unique aspects of the electrochemistry of LIGA through-mask metal deposition and the generation of the fine and uniform microstructures necessary to ensure proper functionality of LIGA components. We draw from both previously published work by external researchers in the field as well as from published and unpublished studies from within Sandia.

  7. Synthesis, Characterization, and Electrochemistry of sigma-Bonded Cobalt Corroles in High Oxidation States.

    PubMed

    Will, Stefan; Lex, Johann; Vogel, Emanuel; Adamian, Victor A.; Van Caemelbecke, Eric; Kadish, Karl M.

    1996-09-11

    The synthesis, electrochemistry, spectroscopy, and structural characterization of two high-valent phenyl sigma-bonded cobalt corroles containing a central cobalt ion in formal +IV and +V oxidation states is presented. The characterized compounds are represented as phenyl sigma-bonded cobalt corroles, (OEC)Co(C(6)H(5)) and [(OEC)Co(C(6)H(5))]ClO(4), where OEC is the trianion of 2,3,7,8,12,13,17,18-octaethylcorrole. The electronic distribution in both molecules is discussed in terms of their NMR and EPR spectroscopic data, magnetic susceptibility, and electrochemistry.

  8. Martian Dust Devil Electron Avalanche Process and Associated Electrochemistry

    NASA Technical Reports Server (NTRS)

    Jackson, Telana L.; Farrell, William M.; Delory, Gregory T.; Nithianandam, Jeyasingh

    2010-01-01

    Mars' dynamic atmosphere displays localized dust devils and larger, global dust storms. Based on terrestrial analog studies, electrostatic modeling, and laboratory work these features will contain large electrostatic fields formed via triboelectric processes. In the low-pressure Martian atmosphere, these fields may create an electron avalanche and collisional plasma due to an increase in electron density driven by the internal electrical forces. To test the hypothesis that an electron avalanche is sustained under these conditions, a self-consistent atmospheric process model is created including electron impact ionization sources and electron losses via dust absorption, electron dissociation attachment, and electron/ion recombination. This new model is called the Dust Devil Electron Avalanche Model (DDEAM). This model solves simultaneously nine continuity equations describing the evolution of the primary gaseous chemical species involved in the electrochemistry. DDEAM monitors the evolution of the electrons and primary gas constituents, including electron/water interactions. We especially focus on electron dynamics and follow the electrons as they evolve in the E field driven collisional gas. When sources and losses are self-consistently included in the electron continuity equation, the electron density grows exponentially with increasing electric field, reaching an equilibrium that forms a sustained time-stable collisional plasma. However, the character of this plasma differs depending upon the assumed growth rate saturation process (chemical saturation versus space charge). DDEAM also shows the possibility of the loss of atmospheric methane as a function of electric field due to electron dissociative attachment of the hydrocarbon. The methane destruction rates are presented and can be included in other larger atmospheric models.

  9. Martian dust devil electron avalanche process and associated electrochemistry

    NASA Astrophysics Data System (ADS)

    Jackson, Telana L.; Farrell, William M.; Delory, Gregory T.; Nithianandam, Jeyasingh

    2010-05-01

    Mars' dynamic atmosphere displays localized dust devils and larger, global dust storms. Based on terrestrial analog studies, electrostatic modeling, and laboratory work, these features will contain large electrostatic fields formed via triboelectric processes. In the low-pressure Martian atmosphere, these fields may create an electron avalanche and collisional plasma due to an increase in electron density driven by the internal electrical forces. To test the hypothesis that an electron avalanche is sustained under these conditions, a self-consistent atmospheric process model is created including electron impact ionization sources and electron losses via dust absorption, electron dissociation attachment, and electron/ion recombination. This new model is called the Dust Devil Electron Avalanche Model (DDEAM). This model solves simultaneously nine continuity equations describing the evolution of the primary gaseous chemical species involved in the electrochemistry. DDEAM monitors the evolution of the electrons and primary gas constituents, including electron/water interactions. We especially focus on electron dynamics and follow the electrons as they evolve in the E field driven collisional gas. When sources and losses are self-consistently included in the electron continuity equation, the electron density grows exponentially with increasing electric field, reaching an equilibrium that forms a sustained time-stable collisional plasma. However, the character of this plasma differs depending upon the assumed growth rate saturation process (chemical saturation versus space charge). DDEAM also shows the possibility of the loss of atmospheric methane as a function of electric field due to electron dissociative attachment of the hydrocarbon. The methane destruction rates are presented and can be included in other larger atmospheric models.

  10. Graphene nanoelectrodes: fabrication and size-dependent electrochemistry.

    PubMed

    Zhang, Bo; Fan, Lixin; Zhong, Huawei; Liu, Yuwen; Chen, Shengli

    2013-07-10

    The fabrication and electrochemistry of a new class of graphene electrodes are presented. Through high-temperature annealing of hydrazine-reduced graphene oxides followed by high-speed centrifugation and size-selected ultrafiltration, flakes of reduced graphene oxides (r-GOs) of nanometer and submicrometer dimensions, respectively, are obtained and separated from the larger ones. Using n-dodecanethiol-modified Au ultramicroelectrodes of appropriately small sizes, quick dipping in dilute suspensions of these small r-GOs allows attachment of only a single flake on the thiol monolayer. The electrodes thus fabricated are used to study the heterogeneous electron transfer (ET) kinetics at r-GOs and the nanoscopic charge transport dynamics at electrochemical interfaces. The r-GOs are found to exhibit similarly high activity for electrochemical ET reactions to metal electrodes. Voltammetric analysis for the relatively slow ET reaction of Fe(CN)6(3-) reduction produces slightly higher ET rate constants at r-GOs of nanometer sizes than at large ones. These ET kinetic features are in accordance with the defect-dominant nature of the r-GOs and the increased defect density in the nanometer-sized flakes as revealed by Raman spectroscopic measurements. The voltammetric enhancement and inhibition for the reduction of Ru(NH3)6(3+) and Fe(CN)6(3-), respectively, at r-GO flakes of submicrometer and nanometer dimensions upon removal of supporting electrolyte are found to significantly deviate in magnitude from those predicted by the electroneutrality-based electromigration theory, which may evidence the increased penetration of the diffuse double layer into the mass transport layer at nanoscopic electrochemical interfaces.

  11. Electrochemistry applied to biomass. Progress report, October 1980-September 1981

    SciTech Connect

    Chum, H. L.

    1982-04-01

    The electrochemical conversion of biomass-derived compounds, obtained through thermochemical pretreatments, into valuable organic chemicals, petrochemical substitutes, and energy-intensive chemicals is investigated. A hardwood-derived lignin obtained from ethanol extraction of the explosively depressurized aspen has been investigated. We have partially characterized this lignin material, and have also submitted it to electrolyses under controlled potential. The electrolytic conditions employed so far affect mainly the carbonyl groups of the ethanol-extracted steam-exploded aspen lignin. We have some evidence of demethoxylation and changed phenolic content after electrolysis. During product isolation, fractionation of the lignin occurs. The material with decreased methoxyl content may be suitable to replace phenol in phenol-formaldehyde-type resins. We are continuing these electrochemical and chemical investigations. Gel-permeation chromatography is being used to separate and characterize the several lignin fractions. In addition, we are carrying out electrolyses under more powerful reducing conditions which may lead to the cleavage of the main bonds in the lignin molecule (the ..beta..-0-4 ether linkages) producing monomeric and dimeric phenolic compounds. The electrochemistry and photoelectrochemistry of levulinic (4-oxo-pentanoic) acid, the major product of controlled degradation of cellulose by acids, have been investigated. This acid can be viewed as a major product of biomass thermochemical pretreatment or as a by-product of acid hydrolysis to fermentable sugars. Since this acid can be present in waste streams of biomass processing, we investigated the photoelectrochemical reactions of this acid on slurries composed of semiconductor/metal particles. The semiconductor investigated was undoped n-TiO/sub 2/, as anatase, anatase-rutile mixture, or rutile.

  12. First principles electrochemistry: Electrons and protons reacting as independent ions

    NASA Astrophysics Data System (ADS)

    Llano, Jorge; Eriksson, Leif A.

    2002-12-01

    We here present a first principles approach to calculate standard Gibbs energies and the corresponding observables (standard electrode potentials in the hydrogen scale ESHE0 and pKa values) of stoichiometric reactions involving electrons and/or protons as independent species in solution, from absolute electrochemical potentials defined according to quantum and statistical mechanics. In order to pass from the conventional electrodic and thermodynamic descriptions of electrochemistry to the first principles approach based on estimating absolute electrochemical potentials, we revisit the problem of the absolute and relative electrochemical scales from the macroscopic and microscopic viewpoints. A microscopic definition of the absolute electrochemical potential is presented in order to enable an identical thermodynamic treatment of any species in a given phase, i.e., electrons, protons, atoms, molecules, atomic and molecular ions, and electronically excited species. We show that absolute standard chemical potentials in the mole fraction scale can be easily computed with wave function and density functional theories in conjunction with self-consistent reaction field models. Based on Boltzmann and Fermi-Dirac statistics and experimental solvation data, we estimate an internally compatible set of absolute standard chemical and electrochemical potentials of protons and solvated electrons in the molality and molarity scales in aqueous solution at 298 K and 1 atm, within an absolute error of ±0.5 kcal/mol. This scheme enables a consistent and simultaneous description of the Gibbs energy changes and the observables (ESHE0 and pKa 's) of electron, proton, and proton-coupled electron transfer reactions in aqueous solution at 298 K and 1 atm.

  13. Martian Dust Devil Electron Avalanche Process and Associated Electrochemistry

    NASA Technical Reports Server (NTRS)

    Jackson, Telana L.; Farrell, William M.; Delory, Gregory T.; Nithianandam, Jeyasingh

    2010-01-01

    Mars' dynamic atmosphere displays localized dust devils and larger, global dust storms. Based on terrestrial analog studies, electrostatic modeling, and laboratory work these features will contain large electrostatic fields formed via triboelectric processes. In the low-pressure Martian atmosphere, these fields may create an electron avalanche and collisional plasma due to an increase in electron density driven by the internal electrical forces. To test the hypothesis that an electron avalanche is sustained under these conditions, a self-consistent atmospheric process model is created including electron impact ionization sources and electron losses via dust absorption, electron dissociation attachment, and electron/ion recombination. This new model is called the Dust Devil Electron Avalanche Model (DDEAM). This model solves simultaneously nine continuity equations describing the evolution of the primary gaseous chemical species involved in the electrochemistry. DDEAM monitors the evolution of the electrons and primary gas constituents, including electron/water interactions. We especially focus on electron dynamics and follow the electrons as they evolve in the E field driven collisional gas. When sources and losses are self-consistently included in the electron continuity equation, the electron density grows exponentially with increasing electric field, reaching an equilibrium that forms a sustained time-stable collisional plasma. However, the character of this plasma differs depending upon the assumed growth rate saturation process (chemical saturation versus space charge). DDEAM also shows the possibility of the loss of atmospheric methane as a function of electric field due to electron dissociative attachment of the hydrocarbon. The methane destruction rates are presented and can be included in other larger atmospheric models.

  14. Towards combined electrochemistry and surface-enhanced resonance Raman of heme proteins: Improvement of diffusion electrochemistry of cytochrome c at silver electrodes chemically modified with 4-mercaptopyridine.

    PubMed

    Millo, Diego; Ranieri, Antonio; Koot, Wynanda; Gooijer, Cees; van der Zwan, Gert

    2006-08-01

    To date, a successful combination of surface-enhanced resonance Raman spectroscopy (SERRS) and electrochemistry to study heme proteins is inhibited by the problems raised by the prerequisite to use silver as electrode metal. This paper indicates an approach to overcome these problems. It describes a quick and reproducible procedure to prepare silver electrodes chemically modified with 4-mercaptopyridine suitable to perform diffusion electrochemistry of cytochrome c (cyt c). The method involves the employment of a mechanical and a chemical treatment and avoids the use of alumina slurries and any electrochemical pretreatment. Cyclic voltammetry (CV) was used to test the electrochemical response of cyt c, and the CV signals were found identical with those obtained on gold electrodes under the same experimental conditions. Compared to previous literature, a significant improvement of the CV signal of cyt c at silver electrodes was achieved. Preliminary results show that this treatment can be also successfully employed for the preparation of SERRS-active electrodes.

  15. In Situ Electrochemistry of Rechargeable Battery Materials: Status Report and Perspectives.

    PubMed

    Yang, Yijun; Liu, Xizheng; Dai, Zhonghua; Yuan, Fangli; Bando, Yoshio; Golberg, Dmitri; Wang, Xi

    2017-08-01

    The development of rechargeable batteries with high performance is considered to be a feasible way to satisfy the increasing needs of electric vehicles and portable devices. It is of vital importance to design electrodes with high electrochemical performance and to understand the nature of the electrode/electrolyte interfaces during battery operation, which allows a direct observation of the complicated chemical and physical processes within the electrodes and electrolyte, and thus provides real-time information for further design and optimization of the battery performance. Here, the recent progress in in situ techniques employed for the investigations of material structural evolutions is described, including characterization using neutrons, X-ray diffraction, and nuclear magnetic resonance. In situ techniques utilized for in-depth uncovering the electrode/electrolyte phase/interface change mechanisms are then highlighted, including transmission electron microscopy, atomic force microscopy, X-ray spectroscopy, and Raman spectroscopy. The real-time monitoring of lithium dendrite growth and in situ detection of gas evolution during charge/discharge processes are also discussed. Finally, the major challenges and opportunities of in situ characterization techniques are outlined toward new developments of rechargeable batteries, including innovation in the design of compatible in situ cells, applications of dynamic analysis, and in situ electrochemistry under multi-stimuli. A clear and in-depth understanding of in situ technique applications and the mechanisms of structural evolutions, surface/interface changes, and gas generations within rechargeable batteries is given here. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Semiconductor electrochemistry of coal pyrite. Technical progress report, January--March 1993

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-05-01

    This project seeks to advance the fundamental understanding of the physicochemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. A novel approach to the study of pyrite aqueous electrochemistry is proposed, based on the use of both synthetic and natural ( i.e. coal-derived) pyrite specimens, the utilization of pyrite both in the form of micro (i.e. colloidal and subcolloidal) and macro (i.e. rotating ring disk) electrodes, and the application of in-situ direct electroanalytical and spectroelectrochemical characterization techniques. The work performed during this quarter focuses on the synthesis of pyrite in aqueous solutions at room temperature and atmospheric pressure. The experimental results show that the initial product from the reaction between ferrous ions and sulfide ions is X-ray amorphous iron sulfide, and the final product is mackinawite from this reaction. Both amorphous iron sulfide and mackinawite in wet states are oxidized quickly in air to {gamma}-FeOOH. Pyrite can form in aqueous solution through a simple path from a reaction between ferric ions and sulfide ions at room temperature within 9 days. It is believed that a redox reaction occurs between ferric and sulfide ions to form ferrous ions and elemental sulfur. The Fe{sup 2+}, S{sup 2{minus}} ions and elemental sulfur, S{sup o}, in the system can then react with each other to form pyrite. This pathway of pyrite formation can be used in synthesizing nanoparticles of pyrite in microemulsions.

  17. Semiconductor electrochemistry of coal pyrite. Technical progress report, October--December 1992

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-02-01

    This project seeks to advance the fundamental understanding of the physics-chemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid minedrainage. A novel approach to the study of pyrite aqueous electrochemistry is proposed, based on the use of both synthetic and natural ( i.e. coal-derived) pyrite specimens, the utilization of.pyrite both in the form of micro (i.e. colloidal and subcolloidal) and macro (i.e. rotating ring disk) electrodes, and the application of in-situ direct electroanalytical and spectroelectrochemical characterization techniques. The kinetic study of the reaction between sulfide and ferrous ions in solution suggested that the black species formed initially is FeHS{sup +} intermediate. To farther confirm this mechanism, the experiments aimed at establishing the stoichiometry for the intermediate were carried out thermodynamically with a stopped-flow spectrophotometric technique. The results showed that the mole ratio of H{sup {minus}}/Fe{sup 2+} is 1 to 1 for the intermediate product, which is in good agreement with the kinetic results previously obtained. Furthermore, the equilibrium constant for the reaction Fe{sup 2+} + H{sup {minus}} = FeHS{sup +} was determined as K = 10{sup 4.34}. The forward rate constant is 10{sup 3.81}(mol/l){sup {minus}1}sec{sup {minus}1} and the backward rate constant is 10{sup {minus}0.53} (mol/l){sup {minus}1} sec{sup {minus}1}.

  18. Evaluation of Tris-Bipyridine Chromium Complexes for Flow Battery Applications: Impact of Bipyridine Ligand Structure on Solubility and Electrochemistry.

    PubMed

    Cabrera, Pablo J; Yang, Xingyi; Suttil, James A; Brooner, Rachel E M; Thompson, Levi T; Sanford, Melanie S

    2015-11-02

    This report describes the design, synthesis, solubility, and electrochemistry of a series of tris-bipyridine chromium complexes that exhibit up to six reversible redox couples as well as solubilities approaching 1 M in acetonitrile. We have systematically modified both the ligand structure and the oxidation state of these complexes to gain insights into the factors that impact solubility and electrochemistry. The results provide a set of structure-solubility-electrochemistry relationships to guide the future development of electrolytes for nonaqueous flow batteries. In addition, we have identified a promising candidate from the series of chromium complexes for further electrochemical and battery assessment.

  19. Inquiry-Based Laboratory Activities in Electrochemistry: High School Students' Achievements and Attitudes

    ERIC Educational Resources Information Center

    Sesen, Burcin Acar; Tarhan, Leman

    2013-01-01

    This study aimed to investigate the effects of inquiry-based laboratory activities on high school students' understanding of electrochemistry and attitudes towards chemistry and laboratory work. The participants were 62 high school students (average age 17 years) in an urban public high school in Turkey. Students were assigned to experimental (N =…

  20. Computer-Animated Instruction and Students' Conceptual Change in Electrochemistry: Preliminary Qualitative Analysis

    ERIC Educational Resources Information Center

    Talib, Othman; Matthews, Robert; Secombe, Margaret

    2005-01-01

    This paper discusses the potential of applying computer-animated instruction (CAnI) as an effective conceptual change strategy in teaching electrochemistry in comparison to conventional lecture-based instruction (CLI). The core assumption in this study is that conceptual change in learners is an active, constructive process that is enhanced by the…

  1. A Historical Analysis of the Daniell Cell and Electrochemistry Teaching in French and Tunisian Textbooks

    ERIC Educational Resources Information Center

    Boulabiar, Ahlem; Bouraoui, Kamel; Chastrette, Maurice; Abderrabba, Manef

    2004-01-01

    The condition in which the Daniell Cell was historically constructed is examined and the evolution of its presentation in French and Tunisian chemistry textbooks is analyzed. Based on the studies, several innovations to facilitate the teaching of the cell, and more generally, the teaching of electrochemistry and of ionic conduction are proposed.

  2. Semiconductor electrochemistry of coal pyrite. Final technical report, September 1990--September 1995

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1996-01-01

    This project is concerned with the physiochemical processes occuring at the pyrite/aqueous interface, in the context of coal cleaning, desulfurization, and acid mine drainage. The use of synthetic particles of pyrite as model electrodes to investigate the semiconductor electrochemistry of pyrite is employed.

  3. Effects of Jigsaw and Animation Techniques on Students' Understanding of Concepts and Subjects in Electrochemistry

    ERIC Educational Resources Information Center

    Doymus, Kemal; Karacop, Ataman; Simsek, Umit

    2010-01-01

    This study investigated the effect of jigsaw cooperative learning and animation versus traditional teaching methods on students' understanding of electrochemistry in a first-year general chemistry course. This study was carried out in three different classes in the department of primary science education during the 2007-2008 academic year. The…

  4. Effect of Cooperative Learning Strategies on Students' Understanding of Concepts in Electrochemistry

    ERIC Educational Resources Information Center

    Acar, Burcin; Tarhan, Leman

    2007-01-01

    The present study was conducted to investigate the degree of effectiveness of cooperative learning instruction over a traditional approach on 11th grade students' understanding of electrochemistry. The study involved forty-one 11th grade students from two science classes with the same teacher. To determine students' misconceptions concerning…

  5. The Effects of Problem-Based Learning (PBL) on the Academic Achievement of Students Studying "Electrochemistry"

    ERIC Educational Resources Information Center

    Günter, Tugçe; Alpat, Sibel Kilinç

    2017-01-01

    This study investigates the effects of problem-based learning (PBL) on students' academic achievements in studying "Electrochemistry" within a course on Analytical Chemistry. The research was of a pretest-posttest control group quasi-experimental design and it was conducted with second year students in the Chemistry Teaching Program at…

  6. A Historical Analysis of the Daniell Cell and Electrochemistry Teaching in French and Tunisian Textbooks

    ERIC Educational Resources Information Center

    Boulabiar, Ahlem; Bouraoui, Kamel; Chastrette, Maurice; Abderrabba, Manef

    2004-01-01

    The condition in which the Daniell Cell was historically constructed is examined and the evolution of its presentation in French and Tunisian chemistry textbooks is analyzed. Based on the studies, several innovations to facilitate the teaching of the cell, and more generally, the teaching of electrochemistry and of ionic conduction are proposed.

  7. Effects of Jigsaw and Animation Techniques on Students' Understanding of Concepts and Subjects in Electrochemistry

    ERIC Educational Resources Information Center

    Doymus, Kemal; Karacop, Ataman; Simsek, Umit

    2010-01-01

    This study investigated the effect of jigsaw cooperative learning and animation versus traditional teaching methods on students' understanding of electrochemistry in a first-year general chemistry course. This study was carried out in three different classes in the department of primary science education during the 2007-2008 academic year. The…

  8. Inquiry-Based Laboratory Activities in Electrochemistry: High School Students' Achievements and Attitudes

    ERIC Educational Resources Information Center

    Sesen, Burcin Acar; Tarhan, Leman

    2013-01-01

    This study aimed to investigate the effects of inquiry-based laboratory activities on high school students' understanding of electrochemistry and attitudes towards chemistry and laboratory work. The participants were 62 high school students (average age 17 years) in an urban public high school in Turkey. Students were assigned to experimental (N =…

  9. Conceptual Difficulties Experienced by Senior High School Students of Electrochemistry: Electrochemical (Galvanic) and Electrolytic Cells.

    ERIC Educational Resources Information Center

    Garnett, Pamela J.; Treagust, David F.

    1992-01-01

    This research used semistructured interviews to investigate students' (n=32) understanding of electrochemistry following a 7-9 week course of instruction. Three misconceptions were identified and incorporated with five previously reported into an alternative framework about electric current involving drifting electrons. Also noted was the tendency…

  10. The Effects of Problem-Based Learning (PBL) on the Academic Achievement of Students Studying "Electrochemistry"

    ERIC Educational Resources Information Center

    Günter, Tugçe; Alpat, Sibel Kilinç

    2017-01-01

    This study investigates the effects of problem-based learning (PBL) on students' academic achievements in studying "Electrochemistry" within a course on Analytical Chemistry. The research was of a pretest-posttest control group quasi-experimental design and it was conducted with second year students in the Chemistry Teaching Program at…

  11. Conceptual Difficulties Experienced by Senior High School Students of Electrochemistry: Electrochemical (Galvanic) and Electrolytic Cells.

    ERIC Educational Resources Information Center

    Garnett, Pamela J.; Treagust, David F.

    1992-01-01

    This research used semistructured interviews to investigate students' (n=32) understanding of electrochemistry following a 7-9 week course of instruction. Three misconceptions were identified and incorporated with five previously reported into an alternative framework about electric current involving drifting electrons. Also noted was the tendency…

  12. A Preliminary Study of Some of the Learning and Assessment Difficulties in Connection with O-Level Electrochemistry.

    ERIC Educational Resources Information Center

    Hillman, R. A. H.; And Others

    1981-01-01

    Describes a study which explored some difficulties related to technical and nontechnical vocabulary and the structure of the examination questions in electrochemistry. Includes results from a sample of 1,500 students in the fourth forms. (DS)

  13. A His-tagged Melanocarpus albomyces laccase and its electrochemistry upon immobilisation on NTA-modified electrodes and in conducting polymer films.

    PubMed

    Sosna, Maciej; Boer, Harry; Bartlett, Philip N

    2013-07-22

    The article describes the construction, immobilisation and electrochemistry of histidine tagged laccase from Melanocarpus albomyces. A facile method of functionalisation of glassy carbon electrodes with nitrilotriacetic acid (NTA) using diazonium grafting and solid state chemistry is described. NTA-modified electrodes are shown to bind laccase which reduces oxygen at neutral pH in the presence of soluble redox mediator. Laccase-modified electrodes are also prepared by enzyme immobilisation within poly(aniline)/poly(vinylsulfonate) films. The polymer is found to efficiently retain the enzyme as well as provide direct electrical contact between the electrode and the enzyme active centre. Cyclic voltammetry reveals the direct electron transfer to the enzyme is dependent on the redox state of the polymer film.

  14. Modeling the Electrochemistry of an SOFC through the Electrodes and Electrolyte

    SciTech Connect

    Ryan, Emily M.; Recknagle, Kurtis P.; Khaleel, Mohammad A.

    2011-12-01

    This paper describes a distributed electrochemistry model of the solid oxide fuel cell (SOFC) electrodes and electrolyte. The distributed electrochemistry (DEC) model solves the transport, reactions, and electric potential through the thickness of the SOFC electrodes. The DEC model allows the local conditions within the electrodes to be studied and allows for a better understanding of how electrochemical and microstructural parameters affect the electrodes. In this paper the governing equations and implementation of the DEC model are presented along with several case studies which are used to investigate the sensitivity of the cathode to the microstructural and electrochemical parameters of the model and to explore methods of improving the electrochemical performance of the SOFC cathode.

  15. Binding of Substrate Locks the Electrochemistry of CRY-DASH into DNA Repair.

    PubMed

    Gindt, Yvonne M; Messyasz, Adriana; Jumbo, Pamela I

    2015-05-12

    VcCry1, a member of the CRY-DASH family, may serve two diverse roles in vivo, including blue-light signaling and repair of UV-damaged DNA. We have discovered that the electrochemistry of the flavin adenine dinucleotide cofactor of VcCry1 is locked to cycle only between the hydroquinone and neutral semiquinone states when UV-damaged DNA is present. Other potential substrates, including undamaged DNA and ATP, have no discernible effect on the electrochemistry, and the kinetics of the reduction is unaffected by damaged DNA. Binding of the damaged DNA substrate determines the role of the protein and prevents the presumed photochemistry required for blue-light signaling.

  16. Surface electrochemistry of mesoporous silicas as a key factor in the design of tailored delivery devices.

    PubMed

    Nieto, Alejandra; Colilla, Montserrat; Balas, Francisco; Vallet-Regí, María

    2010-04-06

    The fundamental mechanisms of biologically active molecule adsorption and release from ordered mesoporous silica are discussed in terms of the variation of surface electrochemistry after functionalization. Specifically, ordered mesoporous SBA-15 has been grafted with aminopropyl, etilenediamine, phosphatoethyl, propyl methacrylate, and carboxylic acid groups at different degrees of functionalization. To test the molecular adsorption and release features, three molecules of clinical interest have been selected, namely, antiresorptive zoledronic acid, amino acid L-tryptophan, and protein bovine serum albumin. Molecular loading and delivery aspects have been studied by emphasizing the host-guest interactions, which determine the adsorption and release behavior. It has been found that careful control of surface electrochemistry by functionalization determines the bioactive molecule adsorption whereas the release can be mainly thought of as a diffusion matter dependent on the surface area and molecule size. This enhanced approach opens up new ways to optimize molecule loading for specific clinical needs.

  17. Proceedings of the conference on electrochemistry of carbon allotropes: Graphite, fullerenes and diamond

    SciTech Connect

    Kinoshita, K.; Scherson, D.

    1998-02-01

    This conference provided an opportunity for electrochemists, physicists, materials scientists and engineers to meet and exchange information on different carbon allotropes. The presentations and discussion among the participants provided a forum to develop recommendations on research and development which are relevant to the electrochemistry of carbon allotropes. The following topics which are relevant to the electrochemistry of carbon allotropes were addressed: Graphitized and disordered carbons, as Li-ion intercalation anodes for high-energy-density, high-power-density Li-based secondary batteries; Carbons as substrate materials for catalysis and electrocatalysis; Boron-doped diamond film electrodes; and Electrochemical characterization and electrosynthesis of fullerenes and fullerene-type materials. Abstracts of the presentations are presented.

  18. A Distributed Electrochemistry Modeling Tool for Simulating SOFC Performance and Degradation

    SciTech Connect

    Recknagle, Kurtis P.; Ryan, Emily M.; Khaleel, Mohammad A.

    2011-10-13

    This report presents a distributed electrochemistry (DEC) model capable of investigating the electrochemistry and local conditions with the SOFC MEA based on the local microstructure and multi-physics. The DEC model can calculate the global current-voltage (I-V) performance of the cell as determined by the spatially varying local conditions through the thickness of the electrodes and electrolyte. The simulation tool is able to investigate the electrochemical performance based on characteristics of the electrode microstructure, such as particle size, pore size, electrolyte and electrode phase volume fractions, and triple-phase-boundary length. It can also investigate performance as affected by fuel and oxidant gas flow distributions and other environmental/experimental conditions such as temperature and fuel gas composition. The long-term objective for the DEC modeling tool is to investigate factors that cause electrode degradation and the decay of SOFC performance which decrease longevity.

  19. Blood Glucose Meters Employing Dynamic Electrochemistry Are Stable against Hematocrit Interference in a Laboratory Setting

    PubMed Central

    Pfützner, Andreas; Musholt, Petra B.; Schipper, Christina; Demircik, Filiz; Hengesbach, Carina; Flacke, Frank; Sieber, Jochen; Forst, Thomas

    2013-01-01

    Background Hematocrit (HCT) is known to be a confounding factor that interferes with many blood glucose (BG) measurement technologies, resulting in wrong readings. Dynamic electrochemistry has been identified as one possible way to correct for these potential deviations. The purpose of this laboratory investigation was to assess the HCT stability of four BG meters known to employ dynamic electrochemistry (BGStar and iBGStar, Sanofi; Wavesense Jazz, AgaMatrix; Wellion Linus, MedTrust) in comparison with three other devices (GlucoDock, Medisana; OneTouch Verio Pro, LifeScan; FreeStyle Freedom InsuLinx, Abbott-Medisense). Methods Venous heparinized blood was immediately aliquoted after draw and manipulated to contain three different BG concentrations (60–90, 130–160, and 280–320 mg/dl) and five different HCT levels (25%, 35%, 45%, 55%, and 60%). After careful oxygenation to normal blood oxygen pressure, each of the resulting 15 different samples was measured six times with three devices and three strip lots of each meter. The YSI Stat 2300 served as laboratory reference method. Stability to HCT influence was assumed when less than 10% difference occurred between the highest and lowest mean glucose deviations in relation to HCT concentrations [hematocrit interference factor (HIF)]. Results Five of the investigated self-test meters showed a stable performance with the different HCT levels tested in this investigation: BGStar (HIF 4.6%), iBGStar (6.6%), Wavesense Jazz (4.1%), Wellion Linus (8.5%), and OneTouch Verio Pro (6.2%). The two other meters were influenced by HCT (FreeStyle InsuLinx 17.8%; GlucoDock 46.5%). Conclusions In this study, meters employing dynamic electrochemistry, as used in the BGStar and iBGStar devices, were shown to correct for potential HCT influence on the meter results. Dynamic electrochemistry appears to be an effective way to handle this interfering condition. PMID:24351179

  20. Direct electrochemistry and electrocatalysis of lobetyolin via magnetic functionalized reduced graphene oxide film fabricated electrochemical sensor.

    PubMed

    Sun, Bolu; Gou, Xiaodan; Bai, Ruibin; Abdelmoaty, Ahmed Attia Ahmed; Ma, Yuling; Zheng, Xiaoping; Hu, Fangdi

    2017-05-01

    A novel lobetyolin electrochemical sensor based on a magnetic functionalized reduced graphene oxide/Nafion nanohybrid film has been introduced in this work. The magnetic functionalized reduced graphene oxide was characterized by fourier transform infrared spectroscopy, atomic force microscope, X-ray diffraction, transmission electron microscopy and thermogravimetric analysis. The scanning electron microscopy characterized the morphology and microstructure of the prepared sensors, and the electrochemical effective surface areas of the prepared sensors were also calculated by chronocoulometry method. The electrochemical behavior of lobetyolin on the magnetic functionalized reduced graphene oxide/Nafion nanohybrid modified glassy carbon electrode was investigated by cyclic voltammetry and differential pulse voltammetry in a phosphate buffer solution of pH6.0. The electron-transfer coefficient (α), electron transfer number (n), and electrode reaction rate constant (Κs) were calculated as 0.78, 0.73, and 4.63s(-1), respectively. Under the optimized conditions, the sensor based on magnetic functionalized reduced graphene oxide/Nafion showed a linear voltammetric response to the lobetyolin concentration at 1.0×10(-7) to 1.0×10(-4)mol/L with detection limit (S/N=3)of 4.3×10(-8)mol/L. The proposed sensor also displayed acceptable reproducibility, long-term stability, and high selectivity, and performs well for analysis of lobetyolin in real samples. The voltammetric sensor was successfully applied to detect lobetyolin in Codonopsis pilosula with recovery values in the range of 96.12%-102.66%.

  1. Characterization, direct electrochemistry, and amperometric biosensing of graphene by noncovalent functionalization with picket-fence porphyrin.

    PubMed

    Tu, Wenwen; Lei, Jianping; Zhang, Siyuan; Ju, Huangxian

    2010-09-17

    Reduced graphene oxide (RGO) was prepared and functionalized with picket-fence porphyrin, 5,10,15,20-tetrakis [αααα-2-trismethylammoniomethylphenyl] porphyrin iron(III) pentachloride (FeTMAPP), through π-π interactions. The resulting nanocomposite was characterized by atomic force microscopy (AFM); transmission electron microscopy (TEM); contact angle measurements; and fluorescence, Raman, and UV/Vis absorption spectroscopy. On account of the introduction of positively charged FeTMAPP, the functionalized RGO showed good dispersion in aqueous solution. The RGO could greatly accelerate the electron transfer of FeTMAPP to produce a well-defined redox couple of Fe(III)/Fe(II) at -0.291 and -0.314 V. Due to the synergic effect between RGO and the porphyrin, the nanocomposite showed excellent electrocatalytic activity toward the reduction of chlorite, thus leading to highly sensitive amperometric biosensing at low applied potential. The biosensor for chlorite showed a linear range from 5.0×10(-8) to 1.2×10(-4) mol L(-1) with a detection limit of 2.4×10(-8) mol L(-1) at a signal-to-noise ratio of 3. The picket-fence porphyrin could serve as an efficient species to functionalize graphene for electronic and optical applications.

  2. Spin-Dependent Transport through Chiral Molecules Studied by Spin-Dependent Electrochemistry

    PubMed Central

    2016-01-01

    Conspectus Molecular spintronics (spin + electronics), which aims to exploit both the spin degree of freedom and the electron charge in molecular devices, has recently received massive attention. Our recent experiments on molecular spintronics employ chiral molecules which have the unexpected property of acting as spin filters, by way of an effect we call “chiral-induced spin selectivity” (CISS). In this Account, we discuss new types of spin-dependent electrochemistry measurements and their use to probe the spin-dependent charge transport properties of nonmagnetic chiral conductive polymers and biomolecules, such as oligopeptides, L/D cysteine, cytochrome c, bacteriorhodopsin (bR), and oligopeptide-CdSe nanoparticles (NPs) hybrid structures. Spin-dependent electrochemical measurements were carried out by employing ferromagnetic electrodes modified with chiral molecules used as the working electrode. Redox probes were used either in solution or when directly attached to the ferromagnetic electrodes. During the electrochemical measurements, the ferromagnetic electrode was magnetized either with its magnetic moment pointing “UP” or “DOWN” using a permanent magnet (H = 0.5 T), placed underneath the chemically modified ferromagnetic electrodes. The spin polarization of the current was found to be in the range of 5–30%, even in the case of small chiral molecules. Chiral films of the l- and d-cysteine tethered with a redox-active dye, toludin blue O, show spin polarizarion that depends on the chirality. Because the nickel electrodes are susceptible to corrosion, we explored the effect of coating them with a thin gold overlayer. The effect of the gold layer on the spin polarization of the electrons ejected from the electrode was investigated. In addition, the role of the structure of the protein on the spin selective transport was also studied as a function of bias voltage and the effect of protein denaturation was revealed. In addition to

  3. Spin-Dependent Transport through Chiral Molecules Studied by Spin-Dependent Electrochemistry.

    PubMed

    Mondal, Prakash Chandra; Fontanesi, Claudio; Waldeck, David H; Naaman, Ron

    2016-11-15

    Molecular spintronics (spin + electronics), which aims to exploit both the spin degree of freedom and the electron charge in molecular devices, has recently received massive attention. Our recent experiments on molecular spintronics employ chiral molecules which have the unexpected property of acting as spin filters, by way of an effect we call "chiral-induced spin selectivity" (CISS). In this Account, we discuss new types of spin-dependent electrochemistry measurements and their use to probe the spin-dependent charge transport properties of nonmagnetic chiral conductive polymers and biomolecules, such as oligopeptides, L/D cysteine, cytochrome c, bacteriorhodopsin (bR), and oligopeptide-CdSe nanoparticles (NPs) hybrid structures. Spin-dependent electrochemical measurements were carried out by employing ferromagnetic electrodes modified with chiral molecules used as the working electrode. Redox probes were used either in solution or when directly attached to the ferromagnetic electrodes. During the electrochemical measurements, the ferromagnetic electrode was magnetized either with its magnetic moment pointing "UP" or "DOWN" using a permanent magnet (H = 0.5 T), placed underneath the chemically modified ferromagnetic electrodes. The spin polarization of the current was found to be in the range of 5-30%, even in the case of small chiral molecules. Chiral films of the l- and d-cysteine tethered with a redox-active dye, toludin blue O, show spin polarizarion that depends on the chirality. Because the nickel electrodes are susceptible to corrosion, we explored the effect of coating them with a thin gold overlayer. The effect of the gold layer on the spin polarization of the electrons ejected from the electrode was investigated. In addition, the role of the structure of the protein on the spin selective transport was also studied as a function of bias voltage and the effect of protein denaturation was revealed. In addition to "dark" measurements, we also describe

  4. Thin-film Electrochemistry of Single Prussian Blue Nanoparticles Revealed by Surface Plasmon Resonance Microscopy.

    PubMed

    Jiang, Dan; Sun, Linlin; Liu, Tao; Wang, Wei

    2017-10-06

    Electrochemical behaviors of Prussian blue (PB) have been intensively studied for decades because it not only serves as a model electro-active nanomaterial in fundamental electrochemistry, but also a promising metal-ion storage electrode material for developing rechargeable batteries. Traditional electrochemical studies are mostly based on bulk materials, leading to an averaged property of billions of PB nanoparticles. In the present work, we employed surface plasmon resonance microscopy (SPRM) to resolve the optical cyclic voltammograms of single PB nanoparticles during electrochemical cycling. It was found that the electrochemical behavior of single PB nanoparticles nicely followed a classical thin-film electrochemistry theory. While kinetic controlled electron transfer was observed at slower scan rates, intra-particle diffusion of K+ ions began to take effect when the scan rate was higher than 60 mV/s. We further found that the electrochemical activity among individual PB nanoparticles was very heterogeneous and such a phenomenon has not been previously observed in the bulk measurements. The present work not only demonstrates the thin-film electrochemical feature of single electro-active nanomaterials for the first time, it also validates the applicability of SPRM technique to investigate a variety of metal ion-storage battery materials, with implications in both fundamental nano-electrochemistry and electro-active materials for sensing and battery applications.

  5. Etude aerodynamique d'un jet turbulent impactant une paroi concave

    NASA Astrophysics Data System (ADS)

    LeBlanc, Benoit

    Etant donne la demande croissante de temperatures elevees dans des chambres de combustion de systemes de propulsions en aerospatiale (turbomoteurs, moteur a reaction, etc.), l'interet dans le refroidissement par jets impactant s'est vu croitre. Le refroidissement des aubes de turbine permet une augmentation de temperature de combustion, ce qui se traduit en une augmentation de l'efficacite de combustion et donc une meilleure economie de carburant. Le transfert de chaleur dans les au bages est influence par les aspects aerodynamiques du refroidissement a jet, particulierement dans le cas d'ecoulements turbulents. Un manque de comprehension de l'aerodynamique a l'interieur de ces espaces confinees peut mener a des changements de transfert thermique qui sont inattendus, ce qui augmente le risque de fluage. Il est donc d'interet pour l'industrie aerospatiale et l'academie de poursuivre la recherche dans l'aerodynamique des jets turbulents impactant les parois courbes. Les jets impactant les surfaces courbes ont deja fait l'objet de nombreuses etudes. Par contre des conditions oscillatoires observees en laboratoire se sont averees difficiles a reproduire en numerique, puisque les structures d'ecoulements impactants des parois concaves sont fortement dependantes de la turbulence et des effets instationnaires. Une etude experimentale fut realisee a l'institut PPRIME a l'Universite de Poitiers afin d'observer le phenomene d'oscillation dans le jet. Une serie d'essais ont verifie les conditions d'ecoulement laminaires et turbulentes, toutefois le cout des essais experimentaux a seulement permis d'avoir un apercu du phenomene global. Une deuxieme serie d'essais fut realisee numeriquement a l'Universite de Moncton avec l'outil OpenFOAM pour des conditions d'ecoulement laminaire et bidimensionnel. Cette etude a donc comme but de poursuivre l'enquete de l'aerodynamique oscillatoire des jets impactant des parois courbes, mais pour un regime d'ecoulement transitoire, turbulent

  6. From mercury to nanosensors: Past, present and the future perspective of electrochemistry in pharmaceutical and biomedical analysis.

    PubMed

    Ozkan, Sibel A; Uslu, Bengi

    2016-10-25

    Polarography was the first developed automated method of voltage-controlled electrolysis with dropping mercury electrode (DME). Then, hanging mercury drop and static mercury drop electrodes were added as an alternative indicator electrode. In this way, polarography turned formally into voltammetry with mercury electrodes in the electroreduction way. Solid electrodes such as noble metal and carbon based electrodes can be used for the investigation of the compounds for both oxidation and reduction directions, which is called voltammetry. The voltammetric and polarographic techniques are more sensitive, reproducible, and easily used electroanalytical methods that can be alternative to more frequently used separation and spectrometric methods. Furthermore, in some cases there is a relationship between voltammetry and pharmaceutical samples, and the knowledge of the mechanism of their electrode reactions can give a useful clue in elucidation of the mechanism of their interaction with living cells. The voltammetric and polarographic analysis of drugs in pharmaceutical preparations are by far the most common use of electrochemistry for analytical pharmaceutical problems. Recent trends and challenges in the electrochemical methods for the detection of DNA hybridization and pathogens are available. Low cost, small sample requirement and possibility of miniaturization justifies their increasing development.

  7. Reconstruction de la surface de Fermi dans l'etat normal d'un supraconducteur a haute Tc: Une etude du transport electrique en champ magnetique intense

    NASA Astrophysics Data System (ADS)

    Le Boeuf, David

    Des mesures de resistance longitudinale et de resistance de Hall en champ magnetique intense transverse (perpendiculaire aux plans CuO2) ont ete effectuees au sein de monocristaux de YBa2Cu3Oy (YBCO) demacles, ordonnes et de grande purete, afin d'etudier l'etat fondamental des supraconducteurs a haute Tc dans le regime sous-dope. Cette etude a ete realisee en fonction du dopage et de l'orientation du courant d'excitation J par rapport a l'axe orthorhombique b de la structure cristalline. Les mesures en champ magnetique intense revelent par suppression de la supraconductivite des oscillations magnetiques des resistances longitudinale et de Hall dans YBa2Cu 3O6.51 et YBa2Cu4O8. La conformite du comportement de ces oscillations quantiques au formalisme de Lifshitz-Kosevich, apporte la preuve de l'existence d'une surface de Fermi fermee a caractere quasi-2D, abritant des quasiparticules coherentes respectant la statistique de Fermi-Dirac, dans la phase pseudogap d'YBCO. La faible frequence des oscillations quantiques, combinee avec l'etude de la partie monotone de la resistance de Hall en fonction de la temperature indique que la surface de Fermi d'YBCO sous-dope comprend une petite poche de Fermi occupee par des porteurs de charge negative. Cette particularite de la surface de Fermi dans le regime sous-dope incompatible avec les calculs de structure de bande est en fort contraste avec la structure electronique presente dans le regime surdope. Cette observation implique ainsi l'existence d'un point critique quantique dans le diagramme de phase d'YBCO, au voisinage duquel la surface de Fermi doit subir une reconstruction induite par l'etablissement d'une brisure de la symetrie de translation du reseau cristallin sous-jacent. Enfin, l'etude en fonction du dopage de la resistance de Hall et de la resistance longitudinale en champ magnetique intense suggere qu'un ordre du type onde de densite (DW) est responsable de la reconstruction de la surface de Fermi. L'analogie de

  8. The electrochemistry of SIMFUEL in dilute alkaline hydrogen peroxide solutions

    NASA Astrophysics Data System (ADS)

    Goldik, Jon

    The work described in this thesis is a study of the electrochemistry of SIMFUEL (SIMulated nuclear FUEL) in dilute, alkaline hydrogen peroxide solutions. In the first set of experiments, the reaction of H2O 2 on SIMFUEL electrodes was studied electrochemically and under open circuit conditions in 0.1 mol L-1 NaCl solutions at pH 9.8. The composition of the oxidized UO2 surface was determined by X-ray photoelectron spectroscopy. Hydrogen peroxide reduction was found to be catalyzed by the formation of a mixed UIV/UV (UO 2+x) surface layer, but to be blocked by the accumulation of UVI species (UO3· yH2O or adsorbed (UO2)2+) on the electrode surface. The formation of this UVI layer blocks both H2O2 reduction and oxidation, thereby inhibiting the potentially rapid H2O2 decomposition reaction to H2O and O2. Decomposition is found to proceed at a rate controlled by the desorption of the adsorbed (UO2)2+ or reduction of adsorbed O2 species. Reduction of (O2) ads is coupled to the slow oxidative dissolution of UO2 and formation of a corrosion product deposit of UO3· yH2O. In the second series of experiments, the electrochemical reduction of hydrogen peroxide on SIMFUEL was studied using the steady-state polarization technique. Kinetic parameters for the reaction, such as Tafel slopes and reaction orders, were determined. The results were interpreted in terms of a chemical-electrochemical mechanism involving UIV/UV donor-acceptor reduction sites. The large values of the Tafel slopes and the fractional reaction orders with respect to H2O2 can be understood in terms of the potential-dependent surface coverage of active sites, similar to that observed in the reduction of hydrogen peroxide on oxidized copper surfaces. The effects of pH over the range 10-13 were also investigated. The H2O 2 reduction currents were nearly independent of pH in the range 10-11, but were slowed at more alkaline values. The change in pH dependence appears to be related to the acid-base properties

  9. Etude d'un systeme de recuperation et de stockage de chaleur pour un systeme eolien-diesel avec stockage d'air comprime

    NASA Astrophysics Data System (ADS)

    Remillon, Thibaut

    La recherche presentee dans ce memoire porte sur les systemes hybrides eolien-diesel avec stockage d'air comprime (SHEDAC) adaptes a la production d'electricite en sites isoles, et plus precisement sur l'apport d'un systeme de recuperation et de stockage de chaleur (TES) au fonctionnement de ces systemes. Le principe de fonctionnement est le suivant. Quand la puissance eolienne est excedentaire par rapport aux besoins de la charge, le surplus d'energie est utilise pour comprimer de l'air. De ce processus resulte un rechauffement de l'air, on choisit d'extraire et de stocker la chaleur separement. Lors de la phase de restitution d'energie, l'air comprime utilise pour suralimenter le moteur thermique est rechauffe en utili sant la chaleur stockee precedemment. Tout au long de l'etude, nous avons seulement pris en compte la chaleur provenant du processus de compression de l'air, et neglige en tous points du systeme les echanges de chaleur avec le milieu exterieur. Pour quantifier l'apport du systeme de stockage de chaleur, nous avons tout d'abord mene une etude bibliographique sur ces systemes, pour identifier les meilleures solutions disponibles. Ensuite, on a modelise une de ces solutions sous Simulink pour etudier son fonctionnement de maniere plus precise. D'autre part, on a modelise un systeme de stockage de chaleur ideal pour quantifier l'apport maximal d'un TES sur les performances du SHEDAC. Nous avons conclu que les TES les plus adaptes aux systemes SHEDAC etaient les solutions actives directes a deux reservoirs, et que, pour beneficier au maximum du systeme de stockage de chaleur, il etait interessant de realiser la detente de l'air comprime stocke dans un moteur a air comprime, pour maximiser la recuperation d'energie mecanique.

  10. Etude sur les tendons en materiaux composites et leur application aux ancrages postcontraints

    NASA Astrophysics Data System (ADS)

    Chennouf, Adil

    L'objectif general de la presente these est d'evaluer le comportement a l'arrachement et au fluage d'ancrages injectes constitues de tendons en materiaux composites afin d'etablir des recommandations plus appropriees et realistes pour le dimensionnement et la conception. Quatre types de tendons en materiaux composites, deux a base de fibres d'aramide et deux a base de fibres de carbone, ont ete utilises dans l'etude. Les travaux de recherche de cette these ont porte notamment sur: (I) Une caracterisation physique et mecanique des tendons en materiaux composites utilises dans l'etude. (II) Une etude en laboratoire sur les coulis de scellement. La premiere etape de cette etude a concerne le developpement d'un coulis de scellement performant adapte aux tendons en materiaux composites et a differentes situations d'injection. La seconde etape a traite des essais de caracterisations physique et mecanique du coulis de scellement developpe comparativement a trois coulis de scellement usuels d'un meme rapport E/L de 0,4. (III) Une etude sur des modeles reduits d'ancrages injectes. (IV) Une etude sur des modeles d'ancrages a grande echelle. La synthese de ces etudes a permis d'enoncer les principales conclusions suivantes: (1) Les valeurs moyennes des charges de rupture des tendons en materiaux composites ont ete de 1% a 29% superieures a celles specifiees par les manufacturiers. (2) L'etude sur les coulis de scellement a permis le developpement de coulis de ciment repondant aux criteres fixes, soient une grande stabilite, une bonne fluidite, une legere expansion et de bonnes caracteristiques mecaniques. (3) Les tendons en materiaux composites ont montre des contraintes d'adherence maximum superieures a celles des tendons en acier. (4) Le type de fibre, la configuration et le fini de surface des tendons en materiaux composites gouvernent leur resistance a l'adherence. (5) L'introduction de sable et d'autres ajouts comme les fines de silice et la poudre d'aluminium au coulis

  11. Singing as a Therapeutic Agent, inThe Etude, 1891-1949.

    PubMed

    Hunter

    1999-01-01

    The Etude music magazine, founded by Theodore Presser, was one of a number of popular music magazines published in the years prior to the establishment of the music therapy profession in 1950. During its publication run from 1883 to 1957, over 100 music therapy related articles appeared, including 13 on the health benefits of singing published between 1891 and 1949. Written by authors with diverse backgrounds, such as the famous Battle Creek, Michigan physician John Harvey Kellogg and Boston music critic Louis C. Elson, the articles contained consistent and adamant support regarding the health benefits of singing. The advantages described were both physical and psychological, and were recommended prophylactically for well persons and therapeutically for ill persons. Although the articles varied in perspective, from philosophical to theoretical to pedagogical, there is a consistent holistic medicine theme that appeared almost ahead of its time and no doubt linked to the push for vocal music education in that era. The importance of The Etude in promulgating ideas that helped shape the early practice of music therapy should not be underestimated. For much of its publication run The Etude was the largest music periodical in print, reaching its peak circulation of 250,000 copies per month in 1924.

  12. Probing the nature of electron transfer in metalloproteins on graphene-family materials as nanobiocatalytic scaffold using electrochemistry

    NASA Astrophysics Data System (ADS)

    Gupta, Sanju; Irihamye, Aline

    2015-03-01

    Graphene-based nanomaterials have shown great promise not only in nanoelectronics due to ultrahigh electron mobility but also as biocatalytic scaffolds owing to irreversible protein surface adsorption and facilitating direct electron transfer. In this work, we synthesized stable dispersions of graphene using liquid-phase exfoliation approach based on non-covalent interactions between graphene and 1-pyrenesulfonic acid sodium salt (Py-1SO3), 1-pyrenemethylamine salt (Py - Me-NH2) and Pluronic® P-123 surfactant using only water as solvent compatible with biomolecules. The resulting graphene nanoplatelets (Gr_LPE) are characterized by a combination of analytical (microscopy and spectroscopy) techniques revealing mono- to few-layer graphene displaying that the exfoliation efficiency strongly depends upon the type of pyrene-based salts and organic surfactants. Moreover being completely water-based approach, we build robust nanoscaffolds of graphene-family nanomaterials (GFNs) namely, monolayer graphene, Gr_LPE (the one prepared with Pluronic® P-123), graphene oxide (GO) and its reduced form (rGO) on glassy carbon electrode surface with three important metalloproteins include cytochrome c (Cyt c) [for electron transfer], myoglobin (Mb) [for oxygen storage] and horseradish peroxidase (HRP) [for catalyzing the biochemical reaction]. In order to demonstrate the nanobiocatalytical activity of these proteins, we used electrochemical interfacial direct electron transfer (DET) kinetics and attempt to determine the rate constant (kET) using two different analytical approaches namely, linear sweep voltammetry and Laviron's theory. We elucidated that all of the metalloproteins retain their structural integrity (secondary structure) upon forming mixtures with GFNs confirmed through optical and vibrational spectroscopy and biological activity using electrochemistry. Among the GFNs studied, Gr-LPE, GO and rGO support the efficient electrical wiring of the redox centers (with an

  13. Nanoscale Electrochemistry of sp(2) Carbon Materials: From Graphite and Graphene to Carbon Nanotubes.

    PubMed

    Unwin, Patrick R; Güell, Aleix G; Zhang, Guohui

    2016-09-20

    Carbon materials have a long history of use as electrodes in electrochemistry, from (bio)electroanalysis to applications in energy technologies, such as batteries and fuel cells. With the advent of new forms of nanocarbon, particularly, carbon nanotubes and graphene, carbon electrode materials have taken on even greater significance for electrochemical studies, both in their own right and as components and supports in an array of functional composites. With the increasing prominence of carbon nanomaterials in electrochemistry comes a need to critically evaluate the experimental framework from which a microscopic understanding of electrochemical processes is best developed. This Account advocates the use of emerging electrochemical imaging techniques and confined electrochemical cell formats that have considerable potential to reveal major new perspectives on the intrinsic electrochemical activity of carbon materials, with unprecedented detail and spatial resolution. These techniques allow particular features on a surface to be targeted and models of structure-activity to be developed and tested on a wide range of length scales and time scales. When high resolution electrochemical imaging data are combined with information from other microscopy and spectroscopy techniques applied to the same area of an electrode surface, in a correlative-electrochemical microscopy approach, highly resolved and unambiguous pictures of electrode activity are revealed that provide new views of the electrochemical properties of carbon materials. With a focus on major sp(2) carbon materials, graphite, graphene, and single walled carbon nanotubes (SWNTs), this Account summarizes recent advances that have changed understanding of interfacial electrochemistry at carbon electrodes including: (i) Unequivocal evidence for the high activity of the basal surface of highly oriented pyrolytic graphite (HOPG), which is at least as active as noble metal electrodes (e.g., platinum) for outer

  14. Impact electrochemistry on screen-printed electrodes for the detection of monodispersed silver nanoparticles of sizes 10-107 nm.

    PubMed

    Nasir, Muhammad Zafir Mohamad; Pumera, Martin

    2016-10-12

    Impact electrochemistry provides a useful alternative technique for the detection of silver nanoparticles in solutions. The combined use of impact electrochemistry on screen-printed electrodes (SPEs) for the successful detection of silver nanoparticles provides an avenue for future on-site, point-of-care detection devices to be made for environmental, medicinal and biological uses. Here we discuss the use of screen-printed electrodes for the detection of well-defined monodispersed silver nanoparticles of sizes 10, 20, 40, 80, and 107 nm.

  15. [Novel Approaches in DNA Methylation Studies - MS-HRM Analysis and Electrochemistry].

    PubMed

    Bartošík, M; Ondroušková, E

    Cytosine methylation in DNA is an epigenetic mechanism regulating gene expression and plays a vital role in cell differentiation or proliferation. Tumor cells often exhibit aberrant DNA methylation, e.g. hypermethylation of tumor suppressor gene promoters. New methods, capable of determining methylation status of specific DNA sequences, are thus being developed. Among them, MS-HRM (methylation-specific high resolution melting) and electrochemistry offer relatively inexpensive instrumentation, fast assay times and possibility of screening multiple samples/DNA regions simultaneously. MS-HRM is due to its sensitivity and simplicity an interesting alternative to already established techniques, including methylation-specific PCR or bisulfite sequencing. Electrochemistry, when combined with suitable electroactive labels and electrode surfaces, has been applied in several unique strategies for discrimination of cytosines and methylcytosines. Both techniques were successfully tested in analysis of DNA methylation within promoters of important tumor suppressor genes and could thus help in achieving more precise diagnostics and prognostics of cancer. Aberrant methylation of promoters has already been described in hundreds of genes associated with tumorigenesis and could serve as important biomarker if new methods applicable into clinical practice are sufficiently advanced.Key words: DNA methylation - 5-methylcytosine - HRM analysis - melting temperature - DNA duplex - electrochemistry - nucleic acid hybridizationThis work was supported by MEYS - NPS I - LO1413.The authors declare they have no potential conflicts of interest concerning drugs, products, or services used in the study.The Editorial Board declares that the manuscript met the ICMJE recommendation for biomedical papers.Submitted: 6. 5. 2016Accepted: 16. 5. 2016.

  16. Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments

    DOE PAGES

    Genorio, Bostjan; Staszak-Jirkovský, Jakub; Assary, Rajeev S.; ...

    2016-02-09

    Efficient chemical transformations in energy conversion and storage systems depend on understanding superoxide anion (O2–) electrochemistry at atomic and molecular levels. Here, in this work, a combination of experimental and theoretical techniques are used for rationalizing, and ultimately understanding, the complexity of superoxide anion (electro)chemistry in organic environments. By exploring the O2 + e– ↔ O2– reaction on well-characterized metal single crystals (Au, Pt, Ir), Pt single crystal modified with a single layer of graphene (Graphene@Pt(111)), and glassy carbon (GC) in 1,2 dimethoxyethane (DME) electrolytes, we demonstrate that (i) the reaction is an outer-sphere process; (ii) the reaction product O2–more » can “attack” any part of the DME molecule, i.e., the C–O bond via nucleophilic reaction and the C–H bond via radical hydrogen abstraction; (iii) the adsorption of carbon-based decomposition products and the extent of formation of a “solid electrolyte interface” (“SEI”) increases in the same order as the reactivity of the substrate, i.e., Pt(hkl)/Ir(hkl) » Au(hkl)/GC > Gaphene@Pt(111); and (iv) the formation of the “SEI” layer leads to irreversible superoxide electrochemistry on Pt(hkl) and Ir(hkl) surfaces. In conclusion, we believe this fundamental insight provides a pathway for the rational design of stable organic solvents that are urgently needed for the development of a new generation of reliable and affordable battery systems.« less

  17. Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments

    SciTech Connect

    Genorio, Bostjan; Staszak-Jirkovský, Jakub; Assary, Rajeev S.; Connell, Justin G.; Strmcnik, Dusan; Diesendruck, Charles E.; Lopes, Pietro P.; Stamenkovic, Vojislav R.; Moore, Jeffrey S.; Curtiss, Larry A.; Markovic, Nenad M.

    2016-02-09

    Efficient chemical transformations in energy conversion and storage systems depend on understanding superoxide anion (O2) electrochemistry at atomic and molecular levels. Here, in this work, a combination of experimental and theoretical techniques are used for rationalizing, and ultimately understanding, the complexity of superoxide anion (electro)chemistry in organic environments. By exploring the O2 + e ↔ O2 reaction on well-characterized metal single crystals (Au, Pt, Ir), Pt single crystal modified with a single layer of graphene (Graphene@Pt(111)), and glassy carbon (GC) in 1,2 dimethoxyethane (DME) electrolytes, we demonstrate that (i) the reaction is an outer-sphere process; (ii) the reaction product O2 can “attack” any part of the DME molecule, i.e., the C–O bond via nucleophilic reaction and the C–H bond via radical hydrogen abstraction; (iii) the adsorption of carbon-based decomposition products and the extent of formation of a “solid electrolyte interface” (“SEI”) increases in the same order as the reactivity of the substrate, i.e., Pt(hkl)/Ir(hkl) » Au(hkl)/GC > Gaphene@Pt(111); and (iv) the formation of the “SEI” layer leads to irreversible superoxide electrochemistry on Pt(hkl) and Ir(hkl) surfaces. In conclusion, we believe this fundamental insight provides a pathway for the rational design of stable organic solvents that are urgently needed for the development of a new generation of reliable and affordable battery systems.

  18. Improvement of capabilities of the Distributed Electrochemistry Modeling Tool for investigating SOFC long term performance

    SciTech Connect

    Gonzalez Galdamez, Rinaldo A.; Recknagle, Kurtis P.

    2012-04-30

    This report provides an overview of the work performed for Solid Oxide Fuel Cell (SOFC) modeling during the 2012 Winter/Spring Science Undergraduate Laboratory Internship at Pacific Northwest National Laboratory (PNNL). A brief introduction on the concept, operation basics and applications of fuel cells is given for the general audience. Further details are given regarding the modifications and improvements of the Distributed Electrochemistry (DEC) Modeling tool developed by PNNL engineers to model SOFC long term performance. Within this analysis, a literature review on anode degradation mechanisms is explained and future plans of implementing these into the DEC modeling tool are also proposed.

  19. Etude theorique des fluctuations structurales dans les composes organiques a dimensionnalite reduite

    NASA Astrophysics Data System (ADS)

    Dumoulin, Benoit

    Les systemes a dimensionnalite reduite constituent maintenant une branche entiere de la physique de la matiere condensee. Cette derniere s'est developpee rapidement au cours des dernieres annees, avec la decouverte des materiaux organiques qui presentent, justement, des proprietes physiques fortement anisotropes. Cette these presente une etude en trois parties de plusieurs composes organiques qui, bien que tres differents du point de vue de leurs compositions chimiques et de leurs proprietes physiques a haute temperature, subissent tous une instabilite structurale a tres basse temperature. De plus, dans chacun des cas, l'instabilite structurale est precedee d'un important regime fluctuatif a partir duquel les proprietes physiques changent de maniere significative. Notre etude suit un ordre chronologique inverse puisque nous nous attardons en premier lieu au cas de composes recemment decouverts: les composes de la famille des (BCPTTF)2X (X = PF6 , AsF6). Ces derniers sont des isolants magnetiques a la temperature ambiante et subissent une instabilite structurale de type spin-Peierls a une temperature appelee TSP. En particulier, nous nous interessons a l'etude des proprietes physiques de ces systemes dans le regime fluctuatif, qui precede cette instabilite. Notre etude theorique nous permet de comprendre en detail comment ces systemes s'approchent de l'instabilite struturale. Dans la seconde partie de cette these, nous etudions le regime fluctuatif (pre-transitionnel) observe experimentalement dans le compose de (TMTTF)2PF6. Ce compose organique, dont la structure s'apparente aux sels de Bechgaard, subit une instabilite de type spin-Peierls a une temperature T SP = 19K. Bien que ce compose possede la particularite d'etre un bon conducteur a la temperature ambiante, il subit une transition de type Mott-Hubbard a une temperature Trho ≈ 220K et devient alors un isolant magnetique, analogue aux composes de la famille des (BCPTTF)2X. Le regime fluctuatif precedant l

  20. Guiding Principles of Hydrogenase Catalysis Instigated and Clarified by Protein Film Electrochemistry.

    PubMed

    Armstrong, Fraser A; Evans, Rhiannon M; Hexter, Suzannah V; Murphy, Bonnie J; Roessler, Maxie M; Wulff, Philip

    2016-05-17

    Protein film electrochemistry (PFE) is providing cutting-edge insight into the chemical principles underpinning biological hydrogen. Attached to an electrode, many enzymes exhibit "reversible" electrocatalytic behavior, meaning that a catalyzed redox reaction appears reversible or quasi-reversible when viewed by cyclic voltammetry. This efficiency is most relevant for enzymes that are inspiring advances in renewable energy, such as hydrogen-activating and CO2-reducing enzymes. Exploiting the rich repertoire of available instrumental methods, PFE experiments yield both a general snapshot and fine detail, all from tiny samples of enzyme. The dynamic electrochemical investigations blaze new trails and add exquisite detail to the information gained from structural and spectroscopic studies. This Account describes recent investigations of hydrogenases carried out in Oxford, including ideas initiated with PFE and followed through with complementary techniques, all contributing to an eventual complete picture of fast and efficient H2 activation without Pt. By immobilization of an enzyme on an electrode, catalytic electron flow and the chemistry controlling it can be addressed at the touch of a button. The buried nature of the active site means that structures that have been determined by crystallography or spectroscopy are likely to be protected, retained, and fully relevant in a PFE experiment. An electrocatalysis model formulated for the PFE of immobilized enzymes predicts interesting behavior and gives insight into why some hydrogenases are H2 producers and others are H2 oxidizers. Immobilization also allows for easy addition and removal of inhibitors along with precise potential control, one interesting outcome being that formaldehyde forms a reversible complex with reduced [FeFe]-hydrogenases, thereby providing insight into the order of electron and proton transfers. Experiments on O2-tolerant [NiFe]-hydrogenases show that O2 behaves like a reversible inhibitor: it

  1. Versatile functionalization of nanoelectrodes by oligonucleotides via pyrrole electrochemistry.

    PubMed

    Descamps, Emeline; Nguyen, Khoa; Bouchain-Gautier, Christelle; Filoramo, Arianna; Goux-Capes, Laurence; Goffman, Marcello; Bourgoin, Jean-Philippe; Mailley, Pascal; Livache, Thierry

    2010-11-15

    Surface modification at the nanometer scale is a challenge for the future of molecular electronics. In particular, the precise anchoring and electrical addressing of biological scaffolds such as complex DNA nanonetworks is of importance for generating bio-directed assemblies of nano-objects for nanocircuit purposes. Herein, we consider the individual modification of nanoelectrodes with different oligonucleotide sequences by an electrochemically driven co-polymerization process of pyrrole and modified oligonucleotide sequences bearing pyrrole monomers. We demonstrate that this one-step technique presents the advantages of simplicity, localization of surface modification, mechanical, biological and chemical stability of the coatings, and high lateral resolution.

  2. Semiconductor electrochemistry of particulate pyrite: Mechanisms and products of dissolution

    SciTech Connect

    Wei, D.; Osseo-Asare, K.

    1997-02-01

    Pyrite dissolution in acidic solution was found to occur via both electrochemical oxidation and chemical decomposition. The mechanism of chemical decomposition of pyrite in acidic solution may involve surface complexation of hydrogen ions. The anodic current of pyrite was observed to be of negligible magnitude in acetonitrile solution compared with that in aqueous solution, which indicated that direct reaction of the holes with S{sub 2}{sup 2{minus}} in the pyrite lattice was not significant and that the dissolution of pyrite required the presence of water. The anodic dissolution products of pyrite in acidic aqueous solution included elemental sulfur which was detected by x-ray diffraction.

  3. DNA Electrochemistry Shows DNMT1 Methyltransferase Hyperactivity in Colorectal Tumors.

    PubMed

    Furst, Ariel L; Barton, Jacqueline K

    2015-07-23

    DNMT1, the most abundant human methyltransferase, is responsible for translating the correct methylation pattern during DNA replication, and aberrant methylation by DNMT1 has been linked to tumorigenesis. We have developed a sensitive signal-on electrochemical assay for the measurement of DNMT1 activity in crude tissue lysates. We have further analyzed ten tumor sets and have found a direct correlation between DNMT1 hyperactivity and tumorous tissue. In the majority of samples analyzed, the tumorous tissue has significantly higher DNMT1 activity than the healthy adjacent tissue. No such correlation is observed in measurements of DNMT1 expression by qPCR, DNMT1 protein abundance by western blotting, or DNMT1 activity using a radiometric DNA labeling assay. DNMT1 hyperactivity can result from both protein overexpression and enzyme hyperactivity. DNMT1 activity measured electrochemically provides a direct measure of activity in cell lysates and, as a result, provides a sensitive and early indication of cancerous transformation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Electrochemistry of nanoscale DNA surface films on carbon.

    PubMed

    Oliveira-Brett, A M; Paquim, A M Chiorcea; Diculescu, V C; Piedade, J A P

    2006-12-01

    A DNA electrochemical biosensor is an integrated receptor-transducer device. The most important step in the development and manufacture of a sensitive DNA-biosensor for the detection of DNA-drug interactions is the immobilization procedure of the nucleic acid probe on the transducer surface. Magnetic A/C Mode atomic force microscopy (MAC Mode AFM) images in air were used to characterize two different procedures for immobilising nanoscale double-stranded DNA (dsDNA) surface films on carbon electrodes. Thin film dsDNA layers presented holes in the dsDNA film that left parts of the electrode surface uncovered while thicker films showed a uniform and complete coverage of the electrode. These two procedures for preparing dsDNA-biosensors were used to study the influence of reactive oxygen species (ROS) in the mechanism of DNA damage by quercetin, a flavonoid, and adriamycin, an anthracycline anticancer drug. The study of quercetin-DNA interactions in the presence of Cu(II) ions indicated that the formation of a quercetin-Cu(II) complex leads to the formation of ROS necessary to react with DNA, disrupting the helix and causing the formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo). Reduced adriamycin radicals are able to directly cause oxidative damage to DNA, generating 8-oxodGuo and ROS are not directly involved in this genomic mutagenic lesion.

  5. Scanning thermo-ionic microscopy for probing local electrochemistry at the nanoscale

    NASA Astrophysics Data System (ADS)

    Eshghinejad, Ahmadreza; Nasr Esfahani, Ehsan; Wang, Peiqi; Xie, Shuhong; Geary, Timothy C.; Adler, Stuart B.; Li, Jiangyu

    2016-05-01

    Conventional electrochemical characterization techniques based on voltage and current measurements only probe faradaic and capacitive rates in aggregate. In this work we develop a scanning thermo-ionic microscopy (STIM) to probe local electrochemistry at the nanoscale, based on imaging of Vegard strain induced by thermal oscillation. It is demonstrated from both theoretical analysis and experimental validation that the second harmonic response of thermally induced cantilever vibration, associated with thermal expansion, is present in all solids, whereas the fourth harmonic response, caused by local transport of mobile species, is only present in ionic materials. The origin of STIM response is further confirmed by its reduced amplitude with respect to increased contact force, due to the coupling of stress to concentration of ionic species and/or electronic defects. The technique has been applied to probe Sm-doped Ceria and LiFePO4, both of which exhibit higher concentrations of mobile species near grain boundaries. The STIM gives us a powerful method to study local electrochemistry with high sensitivity and spatial resolution for a wide range of ionic systems, as well as ability to map local thermomechanical response.

  6. Film Self-Assembly of Oppositely Charged Macromolecules Triggered by Electrochemistry through a Morphogenic Approach.

    PubMed

    Dochter, Alexandre; Garnier, Tony; Pardieu, Elodie; Chau, Nguyet Trang Thanh; Maerten, Clément; Senger, Bernard; Schaaf, Pierre; Jierry, Loïc; Boulmedais, Fouzia

    2015-09-22

    The development of new surface functionalization methods that are easy to use, versatile, and allow local deposition represents a real scientific challenge. Overcoming this challenge, we present here a one-pot process that consists in self-assembling, by electrochemistry on an electrode, films made of oppositely charged macromolecules. This method relies on a charge-shifting polyanion, dimethylmaleic-modified poly(allylamine) (PAHd), that undergoes hydrolysis at acidic pH, leading to an overall switching of its charge. When a mixture of the two polyanions, PAHd and poly(styrenesulfonate) (PSS), is placed in contact with an electrode, where the pH is decreased locally by electrochemistry, the transformation of PAHd into a polycation (PAH) leads to the continuous self-assembly of a nanometric PAH/PSS film by electrostatic interactions. The pH decrease is obtained by the electrochemical oxidation of hydroquinone, which produces protons locally over nanometric distances. Using a negatively charged enzyme, alkaline phosphatase (AP), instead of PSS, this one-pot process allows the creation of enzymatically active films. Under mild conditions, self-assembled PAH/AP films have an enzymatic activity which is adjustable simply by controlling the self-assembly time. The selective functionalization of microelectrode arrays by PAH/AP was achieved, opening the route toward miniaturized biosensors.

  7. Scanning thermo-ionic microscopy for probing local electrochemistry at the nanoscale

    SciTech Connect

    Eshghinejad, Ahmadreza; Nasr Esfahani, Ehsan; Wang, Peiqi; Li, Jiangyu; Xie, Shuhong; Geary, Timothy C.; Adler, Stuart B.

    2016-05-28

    Conventional electrochemical characterization techniques based on voltage and current measurements only probe faradaic and capacitive rates in aggregate. In this work we develop a scanning thermo-ionic microscopy (STIM) to probe local electrochemistry at the nanoscale, based on imaging of Vegard strain induced by thermal oscillation. It is demonstrated from both theoretical analysis and experimental validation that the second harmonic response of thermally induced cantilever vibration, associated with thermal expansion, is present in all solids, whereas the fourth harmonic response, caused by local transport of mobile species, is only present in ionic materials. The origin of STIM response is further confirmed by its reduced amplitude with respect to increased contact force, due to the coupling of stress to concentration of ionic species and/or electronic defects. The technique has been applied to probe Sm-doped Ceria and LiFePO{sub 4}, both of which exhibit higher concentrations of mobile species near grain boundaries. The STIM gives us a powerful method to study local electrochemistry with high sensitivity and spatial resolution for a wide range of ionic systems, as well as ability to map local thermomechanical response.

  8. Experimental analysis, modeling, and optimal control of PEM fuel cell electrochemistry

    NASA Astrophysics Data System (ADS)

    Dhanda, Abhishek

    Polymer Electrolyte Membrane (PEM) fuel cells are touted to play a major role in the green hydrogen based economy. However performance issues need to be addressed for mass commercialization of fuel cells. Besides other factors, slow chemical and electrochemical surface reactions on Pt based catalysts cause large potential loss, and are the primary cause of performance degradation in PEM fuel cells. The kinetics of the oxygen reduction reaction (ORR) at the cathode and the hydrogen oxidation reaction (HOR) at the anode depend on the crystal orientation. Accurate modeling of PEM electrochemistry at the Pt/electrolyte interface requires study of reaction mechanisms on well defined Pt surfaces. In this thesis, electrochemistry on single crystal Pt/Nafion interfaces was studied using a novel experimental setup. Steady state and transient impedance spectroscopy experiments were performed at different operating temperatures. These results are used to derive a kinetic model of the adsorbed species and the overall reaction. Based on such a kinetic model of electrochemical reactions, an approach is presented to improve the time-average performance of PEM fuel cells. Electrochemical kinetic rates depend on operating voltage and current signals. Optimal time varying profile of operating current were derived using variational calculus. Simulation results are presented for demonstrating the application of optimal control approach in reducing carbon monoxide (CO) poisoning in PEM fuel cells.

  9. Integration of electrochemistry in micro-total analysis systems for biochemical assays: recent developments.

    PubMed

    Xu, Xiaoli; Zhang, Song; Chen, Hui; Kong, Jilie

    2009-11-15

    Micro-total analysis systems (microTAS) integrate different analytical operations like sample preparation, separation and detection into a single microfabricated device. With the outstanding advantages of low cost, satisfactory analytical efficiency and flexibility in design, highly integrated and miniaturized devices from the concept of microTAS have gained widespread applications, especially in biochemical assays. Electrochemistry is shown to be quite compatible with microanalytical systems for biochemical assays, because of its attractive merits such as simplicity, rapidity, high sensitivity, reduced power consumption, and sample/reagent economy. This review presents recent developments in the integration of electrochemistry in microdevices for biochemical assays. Ingenious microelectrode design and fabrication methods, and versatility of electrochemical techniques are involved. Practical applications of such integrated microsystem in biochemical assays are focused on in situ analysis, point-of-care testing and portable devices. Electrochemical techniques are apparently suited to microsystems, since easy microfabrication of electrochemical elements and a high degree of integration with multi-analytical functions can be achieved at low cost. Such integrated microsystems will play an increasingly important role for analysis of small volume biochemical samples. Work is in progress toward new microdevice design and applications.

  10. Electrochemistry coupled to (LC-)MS for the simulation of oxidative biotransformation reactions of PAHs.

    PubMed

    Wigger, Tina; Seidel, Albrecht; Karst, Uwe

    2017-02-27

    Electrochemistry coupled to liquid chromatography and mass spectrometry was used for simulating the biological and environmental fate of polycyclic aromatic hydrocarbons (PAHs) as well as for studying the PAH degradation behavior during electrochemical remediation. Pyrene and benzo[a]pyrene were selected as model compounds and oxidized within an electrochemical thin-layer cell equipped with boron-doped diamond electrode. At potentials of 1.2 and 1.6 V vs. Pd/H2, quinones were found to be the major oxidation products for both investigated PAHs. These quinones belong to a large group of PAH derivatives referred to as oxygenated PAHs, which have gained increasing attention in recent years due to their high abundance in the environment and their significant toxicity. Separation of oxidation products allowed the identification of two pyrene quinone and three benzo[a]pyrene quinone isomers, all of which are known to be formed via photooxidation and during mammalian metabolism. The good correlation between electrochemically generated PAH quinones and those formed in natural processes was also confirmed by UV irradiation experiments and microsomal incubations. At potentials higher than 2.0 V, further degradation of the initial oxidation products was observed which highlights the capability of electrochemistry to be used as remediation technique.

  11. Effects of Lecture Method Supplemented with Music and Computer Animation on Senior Secondary School Students' Academic Achievement in Electrochemistry

    ERIC Educational Resources Information Center

    Akpoghol, T. V.; Ezeudu, F. O.; Adzape, J. N.; Otor, E. E.

    2016-01-01

    The study investigated the effects of Lecture Method Supplemented with Music (LMM) and Computer Animation (LMC) on senior secondary school students' academic achievement in electrochemistry in Makurdi metropolis. Six research questions and six hypotheses guided the study. The design of the study was quasi experimental, specifically the pre-test,…

  12. Impact of Interactive Multimedia Module with Pedagogical Agents on Students' Understanding and Motivation in the Learning of Electrochemistry

    ERIC Educational Resources Information Center

    Osman, Kamisah; Lee, Tien Tien

    2014-01-01

    The Electrochemistry topic is found to be difficult to learn due to its abstract concepts involving macroscopic, microscopic, and symbolic representation levels. Studies have shown that animation and simulation using information and communication technology (ICT) can help students to visualize and hence enhance their understanding in learning…

  13. Relative Effect of Lecture Method Supplemented with Music and Computer Animation on Senior Secondary School Students' Retention in Electrochemistry

    ERIC Educational Resources Information Center

    Akpoghol, T. V.; Ezeudu, F. O.; Adzape, J. N.; Otor, E. E.

    2016-01-01

    The study investigated the effects of Lecture Method Supplemented with Music (LMM) and Computer Animation (LMC) on senior secondary school students' retention in electrochemistry in Makurdi metropolis. Three research questions and three hypotheses guided the study. The design of the study was quasi experimental, specifically the pre-test,…

  14. Effectiveness of Interactive Multimedia Module with Pedagogical Agent (IMMPA) in the Learning of Electrochemistry: A Preliminary Investigation

    ERIC Educational Resources Information Center

    Lee, Tien Tien; Osman, Kamisah

    2011-01-01

    Electrochemistry is found to be a difficult topic to learn due to its abstract concepts that involve the macroscopic, microscopic and symbolic representation levels. Research showed that animation and simulation using Information and Communication Technology (ICT) can help students to visualize and hence enhance students' understanding in learning…

  15. Impact of Interactive Multimedia Module with Pedagogical Agents on Students' Understanding and Motivation in the Learning of Electrochemistry

    ERIC Educational Resources Information Center

    Osman, Kamisah; Lee, Tien Tien

    2014-01-01

    The Electrochemistry topic is found to be difficult to learn due to its abstract concepts involving macroscopic, microscopic, and symbolic representation levels. Studies have shown that animation and simulation using information and communication technology (ICT) can help students to visualize and hence enhance their understanding in learning…

  16. The Effect of Process Oriented Guided Inquiry Learning (POGIL) on 11th Graders' Conceptual Understanding of Electrochemistry

    ERIC Educational Resources Information Center

    Sen, Senol; Yilmaz, Ayhan; Geban, Ömer

    2016-01-01

    The purpose of this study was to investigate the effect of Process Oriented Guided Inquiry Learning (POGIL) method compared to traditional teaching method on 11th grade students' conceptual understanding of electrochemistry concepts. Participants were 115 students from a public school in Turkey. Nonequivalent control group design was used. Two…

  17. Introducing Students to Inner Sphere Electron Transfer Concepts through Electrochemistry Studies in Diferrocene Mixed-Valence Systems

    ERIC Educational Resources Information Center

    Ventura, Karen; Smith, Mark B.; Prat, Jacob R.; Echegoyen, Lourdes E.; Villagran´, Dino

    2017-01-01

    We have designed a 4 h physical chemistry laboratory to introduce upper division students to electrochemistry concepts, including mixed valency and electron transfer (ET), using cyclic and differential pulse voltammetries. In this laboratory practice, students use a ferrocene dimer consisting of two ferrocene centers covalently bonded through a…

  18. Determination of humic substances in seawater by electrochemistry (mechanisms)

    SciTech Connect

    Quentel, F.; Madec, C.; Courtot-Coupez, J.

    1987-01-01

    A new method for the measurement of the concentration of humic substances (HS) in seawater is described. The peak obtained by differential cathodic sweep voltammetry after HS adsorption in the presence of traces of molybdenum(VI) can be used for quantitative determination. Measurements using various electrochemical techniques, alternating current polarography, cyclic voltammetry, and adsorptive differential pulse voltammetry, would indicate that the film adsorbed onto the electrode is the result of the adsorption of the organic substance in a first step followed in a subsequent step by the formation of a surface complex (Mo(VI)-HS)/sub ads/ rather than the direct adsorption of the dissolved complex. The electrochemical mechanism corresponds to a one-electron reduction of the adsorbed (Mo(VI)-HS)/sub ads/complex to the corresponding (Mo(V)-HS)/sub ads/ complex. 15 references, 6 figures.

  19. Ferrocenyl-phosphonium ionic liquids - synthesis, characterisation and electrochemistry.

    PubMed

    Kübler, Paul; Sundermeyer, Jörg

    2014-03-07

    New unsymmetrically substituted ferrocenyl-phosphonium ionic liquids (ILs) [FcPR2R']NTf2 are synthesized by two or three step syntheses starting from ferrocene, Fc = (C5H5)Fe(C5H4); R = Me, (n)Bu, (n)Hex, Ph; R' = Me, (n)Pr, (n)Bu, Ph; NTf2 = N(SO2CF3)2. The selective synthesis of alkyl phosphines FcPR2via a Friedel-Crafts phosphorylation is highlighted as an alternative for the standard protocol commonly used for ferrocenyl arylphosphines involving lithiation of FcH followed by phosphorylation. The influence of the P-substituents on thermal stability, electrochemical potential, chemical shift, and UV-Vis absorption behavior of the ILs is studied. The phosphonium group acts both as an ionic tag and as an electron-withdrawing substituent directly bound at the Cp-ring position. Therefore the title compounds are attractive for further studies to use them as tunable redox mediators for (photo)electrochemical devices such as dye sensitized solar cells (DSSCs) or redox flow batteries.

  20. Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase.

    PubMed

    Wu, Sheng-Yi; Rothery, Richard A; Weiner, Joel H

    2015-10-09

    We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser(719), NarG-His(1163), and NarG-His(1184)); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His(1092) and NarG-His(1098)). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of -88 and -36 mV, respectively). Ala variants of His(1092) and His(1098) also elicit large ΔEm values of -143 and -101 mV, respectively. An Arg variant of His(1092) elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  1. Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase*

    PubMed Central

    Wu, Sheng-Yi; Rothery, Richard A.; Weiner, Joel H.

    2015-01-01

    We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser719, NarG-His1163, and NarG-His1184); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His1092 and NarG-His1098). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of −88 and −36 mV, respectively). Ala variants of His1092 and His1098 also elicit large ΔEm values of −143 and −101 mV, respectively. An Arg variant of His1092 elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. PMID:26297003

  2. Contributions a L'etude de Dispositifs D'optique Integree

    NASA Astrophysics Data System (ADS)

    Touam, Tahar

    Cette these contient des contributions a l'etude de deux champs du vaste domaine de l'optique integree. A cet effet, nous avons divise notre travail en deux grandes parties:. Dans une premiere partie, nous traitons le probleme de la realisation d'une nouvelle classe de guides d'onde planaires utilisables dans le domaine de longueur d'onde de l'infrarouge moyen (infrarouge thermique), domaine ou l'apparition anticipee de fibres optiques a pertes extremement faibles rendraient fort interessante l'existence de tels guides d'onde planaires. Dans un premier temps, nous presentons une etude analytique originale d'une structure planaire a profil d'indice gradue, suivie d'une analyse d'un guide canal base sur cette structure. Dans un deuxieme temps, nous decrivons le procede de fabrication par pulverisation atomique d'un guide planaire forme d'arseniure de gallium (AsGa) sur du dioxyde de silicium (SiO_2 ), combinaison de materiau compatible avec l'infrarouge moyen. Finalement, nous presentons une etude de conception d'un reseau de surface destine a coupler la lumiere dans un tel guide, les autres methodes traditionnelles de couplage semblant peu appropriees aux environs de lambda = 10 mum. Dans une deuxieme partie, nous traitons le probleme de la jonction Y en optique integree, jonction qui soufre de pertes tres importantes des que l'angle d'ouverture devient interessant pour le concepteur de circuits integres optiques. L'analyse est basee sur la methode numerique dite BPM (Beam Propagation Method; methode de propagation du faisceau) qui fait l'objet d'un bref rappel. Nous poursuivons avec l'etude et l'optimisation d'une nouvelle jonction Y dont l'essence est l'utilisation du phenomene de diffraction a travers trois fentes de phase. Nous obtenons ainsi une tres bonne jonction, separant proprement le faisceau, a une ouverture de 10 degres. Finalement, nous faisons un rappel d'un profil d'indice dit "ideal" pour guides courbes et nous proposons l'utilisation de tels guides

  3. Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media [Water as Promoter and Catalyst in Dioxygen Electrochemistry at Aqueous and Organic Electrified Interfaces].

    DOE PAGES

    Staszak-Jirkovský, Jakub; Subbaraman, Ram; Strmcnik, Dusan; ...

    2015-11-06

    Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultradry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad···H2O (aqueous solutions) and LiO2···H2O (organic solvents) complexes that place water in a configurationally favorable position for proton transfer to weakly adsorbed intermediates. We also find that, even atmore » low concentrations (<10 ppm), water acts simultaneously as a promoter and as a catalyst in the production of Li2O2, regenerating itself through a sequence of steps that include the formation and recombination of H+ and OH-. We conclude that, although the binding energy between metal surfaces and oxygen intermediates is an important descriptor in electrocatalysis, understanding the role of water as a proton-donor reactant may explain many anomalous features in electrocatalysis at metal-liquid interfaces.« less

  4. In-situ Raman spectroscopy to elucidate the influence of adsorption in graphene electrochemistry

    NASA Astrophysics Data System (ADS)

    van den Beld, Wesley T. E.; Odijk, Mathieu; Vervuurt, René H. J.; Weber, Jan-Willem; Bol, Ageeth A.; van den Berg, Albert; Eijkel, Jan C. T.

    2017-03-01

    Electrochemistry on graphene is of particular interest due to graphene’s high surface area, high electrical conductivity and low interfacial capacitance. Because the graphene Fermi level can be probed by its strong Raman signal, information on the graphene doping can be obtained which in turn can provide information on adsorbed atoms or molecules. For this paper, the adsorption analysis was successfully performed using three electroactive substances with different electrode interaction mechanisms: hexaammineruthenium(III) chloride (RuHex), ferrocenemethanol (FcMeOH) and potassium ferricyanide/potassium ferrocyanide (Fe(CN)6). The adsorption state was probed by analysing the G-peak position in the measured in-situ Raman spectrum during electrochemical experiments. We conclude that electrochemical Raman spectroscopy on graphene is a valuable tool to obtain in-situ information on adsorbed species on graphene, isolated from the rest of the electrochemical behaviour.

  5. In Situ, Real-Time Visualization of Electrochemistry Using Magnetic Resonance Imaging.

    PubMed

    Britton, Melanie M; Bayley, Paul M; Howlett, Patrick C; Davenport, Alison J; Forsyth, Maria

    2013-09-05

    The drive to develop better electrochemical energy storage devices requires the development of not only new materials, but also better understanding of the underpinning chemical and dynamical processes within such devices during operation, for which new analytical techniques are required. Currently, there are few techniques that can probe local composition and transport in the electrolyte during battery operation. In this paper, we report a novel application of magnetic resonance imaging (MRI) for probing electrochemical processes in a model electrochemical cell. Using MRI, the transport and zinc and oxygen electrochemistry in an alkaline electrolyte, typical of that found in zinc-air batteries, are investigated. Magnetic resonance relaxation maps of the electrolyte are used to visualize the chemical composition and electrochemical processes occurring during discharge in this model metal-air battery. Such experiments will be useful in the development of new energy storage/conversion devices, as well as other electrochemical technologies.

  6. Bimetallic alloys in action: dynamic atomistic motifs for electrochemistry and catalysis.

    PubMed

    Mueller, Jonathan E; Krtil, Petr; Kibler, Ludwig A; Jacob, Timo

    2014-08-07

    Bimetallic alloys show great promise for applications in a wide range of technologies related to electrochemistry and heterogeneous catalysis. The alloyed nature of these materials supports the existence of surface phenomena and structural motifs not present in single-component materials. These novel features result in electrochemical and catalytic behaviors, requiring entirely new categories of explanations. In this perspective concrete examples are used to illustrate several of these chemical and structural features, which are unique to multi-component metal surfaces. The influence of the surface's structure and surroundings (e.g. adsorbates) on each other provides a common thread, with the emergence of dynamic surfaces as its terminus. In considering three model systems (PtRu, PtNi and AuPd), we discuss not only a selection of surface phenomena relevant to each, but also the implications of these alloy-related behaviors for the electrochemical and catalytic properties of each surface.

  7. On the importance of identifying, characterizing, and predicting fundamental phenomena towards microbial electrochemistry applications.

    PubMed

    Torres, César Iván

    2014-06-01

    The development of microbial electrochemistry research toward technological applications has increased significantly in the past years, leading to many process configurations. This short review focuses on the need to identify and characterize the fundamental phenomena that control the performance of microbial electrochemical cells (MXCs). Specifically, it discusses the importance of recent efforts to discover and characterize novel microorganisms for MXC applications, as well as recent developments to understand transport limitations in MXCs. As we increase our understanding of how MXCs operate, it is imperative to continue modeling efforts in order to effectively predict their performance, design efficient MXC technologies, and implement them commercially. Thus, the success of MXC technologies largely depends on the path of identifying, understanding, and predicting fundamental phenomena that determine MXC performance. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. The edge- and basal-plane-specific electrochemistry of a single-layer graphene sheet

    PubMed Central

    Yuan, Wenjing; Zhou, Yu; Li, Yingru; Li, Chun; Peng, Hailin; Zhang, Jin; Liu, Zhongfan; Dai, Liming; Shi, Gaoquan

    2013-01-01

    Graphene has a unique atom-thick two-dimensional structure and excellent properties, making it attractive for a variety of electrochemical applications, including electrosynthesis, electrochemical sensors or electrocatalysis, and energy conversion and storage. However, the electrochemistry of single-layer graphene has not yet been well understood, possibly due to the technical difficulties in handling individual graphene sheet. Here, we report the electrochemical behavior at single-layer graphene-based electrodes, comparing the basal plane of graphene to its edge. The graphene edge showed 4 orders of magnitude higher specific capacitance, much faster electron transfer rate and stronger electrocatalytic activity than those of graphene basal plane. A convergent diffusion effect was observed at the sub-nanometer thick graphene edge-electrode to accelerate the electrochemical reactions. Coupling with the high conductivity of a high-quality graphene basal plane, graphene edge is an ideal electrode for electrocatalysis and for the storage of capacitive charges. PMID:23896697

  9. Semiconductor electrochemistry of coal pyrite. Technical progress report, October--December 1993

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1994-03-01

    The effects of the semiconductor properties of pyrite on its electrochemical behavior have been explored with the aid of energy level diagram which illustrate the relationship between the energy levels of the solid land the equilibrium potentials of the redox couples in the aqueous solution. A novel approach to the study of pyrite electrochemistry was initiated. This approach is based on pyrite microelectrodes synthesized via aqueous phase precipitation. Preliminary results show that photocurrents can be generated by illumination of the pyrite particles synthesized in our laboratory. Central to this research is the recognition that pyrite is a semiconductor material. (Photo) electrochemical experiments are conducted to unravel the mechanisms of anodic and cathodic processes such as those associated with pyrite decomposition and the reduction of oxidants such as molecular oxygen and the ferric ion.

  10. A review about the surface resistance technique in electrochemistry [review article

    NASA Astrophysics Data System (ADS)

    Tucceri, R.

    2004-12-01

    The use of the surface resistance changes as an alternative method to study the electrochemical interface is reviewed considering both experimental and theoretical aspects. Particular emphasis is laid on the effect of the adsorption on the resistance of thin film electrodes, including adsorption processes of ions, organic compounds, oxygen, hydrogen and underpotential deposition. Relevant and recent experiments, where the technique was used to detect small quantities of cations in solution and redox sites distributions at the metal-polymer interface are also considered. Morphology changes and roughening and corrosion processes of electrode surfaces studied by resistance measurements are also reviewed. Results obtained by coupling surface resistance with both optical methods and Hall effect in electrochemistry, and the important problem of the electrode emersion are also described. Scattering models to explain surface resistance changes are outlined on the basis of their phenomenological parameters, which can be determined by electrochemical measurements.

  11. Critical transport rates that limit the performance of microbial electrochemistry technologies.

    PubMed

    Popat, Sudeep C; Torres, César I

    2016-09-01

    Microbial electrochemistry technologies (METs) take advantage of the connection of microorganisms with electrodes. In the classic case of a microbial anode, the maximization of current density produced is often the goal. But, current production is dependent on many transport processes occurring, which can be rate-limiting. These include the fluxes of electron donor and acceptor, the ionic flux, the acidity and alkalinity fluxes at anode and cathode respectively, the electron transport flux at the biofilm, and the reactant/product crossover flux. Associated with these fluxes are inherent concentration gradients that can affect performance. This critical review provides an analysis on how these transport processes have hindered the development of METs, and how MET designs have evolved as more knowledge of these transport limitations is gained. Finally, suggestions are provided on how to design MET systems taking into consideration critical transport processes that are intimately linked to the current produced.

  12. Two-Step Bipolar Electrochemistry: Generation of Composition Gradient and Visual Screening of Electrocatalytic Activity.

    PubMed

    Termebaf, Hajar; Shayan, Mohsen; Kiani, Abolfazl

    2015-12-08

    Bipolar electrochemistry (BE) is employed for both creating electrocatalysts composition gradient and visual screening of the prepared composition on a single substrate in just two experiment runs. In a series of proof-of-principle experiments, we demonstrate gradient electrodeposition of Ni-Cu using BE; then the electrocatalytic activity of the prepared composition gradient toward the hydrogen evolution reaction (HER) is visually screened in the BE system using array of BPEs. Moreover, the morphology and the chemical composition of the Ni-Cu gradient are screened along the length of the bipolar electrode (BPE). By measuring the potential gradient over the BPE, it is also demonstrated that by controlling the concentration of the metals precursor and the supporting electrolyte, the length of the bipolar electrodeposited gradient can be controlled.

  13. In-situ Raman spectroscopy to elucidate the influence of adsorption in graphene electrochemistry

    PubMed Central

    van den Beld, Wesley T. E.; Odijk, Mathieu; Vervuurt, René H. J.; Weber, Jan-Willem; Bol, Ageeth A.; van den Berg, Albert; Eijkel, Jan C. T.

    2017-01-01

    Electrochemistry on graphene is of particular interest due to graphene’s high surface area, high electrical conductivity and low interfacial capacitance. Because the graphene Fermi level can be probed by its strong Raman signal, information on the graphene doping can be obtained which in turn can provide information on adsorbed atoms or molecules. For this paper, the adsorption analysis was successfully performed using three electroactive substances with different electrode interaction mechanisms: hexaammineruthenium(III) chloride (RuHex), ferrocenemethanol (FcMeOH) and potassium ferricyanide/potassium ferrocyanide (Fe(CN)6). The adsorption state was probed by analysing the G-peak position in the measured in-situ Raman spectrum during electrochemical experiments. We conclude that electrochemical Raman spectroscopy on graphene is a valuable tool to obtain in-situ information on adsorbed species on graphene, isolated from the rest of the electrochemical behaviour. PMID:28338094

  14. The electrochemistry in 316SS crevices exposed to PWR-relevant conditions

    NASA Astrophysics Data System (ADS)

    Vankeerberghen, M.; Weyns, G.; Gavrilov, S.; Henshaw, J.; Deconinck, J.

    2009-04-01

    The chemical and electrochemical conditions within a crevice of Type 316 stainless steel in boric acid-lithium hydroxide solutions under PWR-relevant conditions were modelled with a computational electrochemistry code. The influence of various variables: dissolved hydrogen, boric acid, lithium hydroxide concentration, crevice length, and radiation dose rate was studied. It was found with the model that 25 ccH 2/kg (STP) was sufficient to remain below an electrode potential of -230 mV she, commonly accepted sufficient to prevent stress corrosion cracking under BWR conditions. In a PWR plant various operational B-Li cycles are possible but it was found that the choice of the cycle did not significantly influence the model results. It was also found that a hydrogen level of 50 ccH 2/kg (STP) would be needed to avoid substantial lowering of the pH inside a crevice.

  15. Condensed Matter and Material Sciences: Electrochemistry of Immobilized Particles and Droplets

    NASA Astrophysics Data System (ADS)

    Scholz, Fritz; Schröder, Uwe; Gulaboski, Rubin

    Immobilizing particles or droplets on electrodes is a novel and most powerful technique for studying the electrochemical reactions of three-phase systems. It gives access to a wealth of information, ranging from quantitative and phase analysis to thermodynamic and kinetic data of electrode processes. Three-phase electrodes with immobilized droplets provide information on the electrochemistry of redox liquids and of compounds dissolved in inert organic liquids. Such measurements allow the determination of the Gibbs energies of the transfer of cations and anions between immiscible solvents, and thus make it possible to assess the hydrophobicity of ions -- a property that is of great importance for pharmaceutical applications, biological studies, and for many fields of chemistry.

  16. Electrochemistry of thin-plate lead-carbon batteries employing alternative current collectors

    NASA Astrophysics Data System (ADS)

    Lannelongue, Jérémy; Cugnet, Mikael; Guillet, Nicolas; Kirchev, Angel

    2017-06-01

    The article discusses the electrochemistry of lead-carbon battery cells based on thin-plate electrodes with alternative current collectors. The latter are comprised of lead-electroplated graphite foil and expanded titanium mesh coated with SnO2 replacing the conventional negative and positive grids. The results from charge/discharge tests, cycling voltammetry and impedance spectroscopy measurements show that the negative electrodes store energy via three types of electrochemical processes: electrostatic storage, reversible hydrogen storage and precipitation/dissolution of lead and lead sulfate. When the activated carbon is the predominant component of the negative active material the preferred energy storage mechanism is the reversible hydrogen storage. The use of titanium as alternative current collector allows to increase the active material to current collector ratio to 5: 1, retaining a high power performance and increasing the battery lifetime beyond 3000 equivalent cycles in partial state of charge cycling applications.

  17. Applications of the Lithium Focused Ion Beam: Nanoscale Electrochemistry and Microdisk Mode Imaging

    NASA Astrophysics Data System (ADS)

    McGehee, William; Takeuchi, Saya; Michels, Thomas; Oleshko, Vladimir; Aksyuk, Vladimir; Soles, Christopher; McClelland, Jabez; CenterNanoscale Science; Technology at NIST Collaboration; Materials Measurement Laboratory at NIST Collaboration

    2016-05-01

    The NIST-developed lithium Focused-Ion-Beam (LiFIB) system creates a low-energy, picoampere-scale ion beam from a photoionized gas of laser-cooled atoms. The ion beam can be focused to a <30 nm spot and scanned across a sample. This enables imaging through collection of ion-induced secondary electrons (similar to SEM) as well as the ability to selectively deposit lithium-ions into nanoscale volumes in a material. We exploit this second ability of the LiFIB to selectively ''titrate'' lithium ions as a means of probing the optical modes in microdisk resonators as well as for exploring nanoscale, Li-ion electrochemistry in battery-relevant materials. We present an overview of both measurements, including imaging of the optical mode in a silicon microdisk and a comparison of FIB and electrochemical lithiation of tin.

  18. Ubiquitous trisulfur radical anion: fundamentals and applications in materials science, electrochemistry, analytical chemistry and geochemistry.

    PubMed

    Chivers, Tristram; Elder, Philip J W

    2013-07-21

    The trisulfur radical anion [S3]˙(-) is well-known from inorganic chemistry textbooks as the blue chromophore in ultramarine blues in which this highly reactive species is trapped in a zeolitic framework. Recent findings have revealed that [S3]˙(-) has a multi-faceted role in a variety of media, including alkali metal-sulfur batteries, aqueous solutions at high temperatures and pressures, and ionic liquids; it has also been used to detect trace amounts of water in organic solvents. This tutorial review illustrates how various physical techniques are used to identify a reactive species in solution and shows how elucidation of electronic structures can be used to explain spectroscopic and structural properties. Examples of the function of [S3]˙(-) in materials science, electrochemistry, analytical chemistry and geochemistry are used to illustrate the widespread influence of this fundamentally important triatomic sulfur species.

  19. On-line electrochemistry/liquid chromatography/mass spectrometry for the simulation of pesticide metabolism.

    PubMed

    Lohmann, Wiebke; Dötzer, Reinhard; Gütter, Gerald; Van Leeuwen, Suze M; Karst, Uwe

    2009-01-01

    On-line electrochemistry/liquid chromatography/mass spectrometry (EC/LC/MS) was employed to mimic the oxidative metabolism of the fungicide boscalid. High-resolution mass spectrometry and MS/MS experiments were used to identify its electrochemical oxidation products. Furthermore, the introduction of a second electrochemical cell with reductive conditions provided important additional information on the oxidation products. With this equipment, hydroxylation, dehydrogenation, formation of a covalent ammonia adduct, and dimerization were detected after initial one-electron oxidation of boscalid to a radical cation. On-line reaction with glutathione yielded different isomeric covalent glutathione adducts. The results of the electrochemical oxidation are in good accordance with previously reported in vivo experiments, showing that EC/LC/MS is a useful tool for studying biotransformation reactions of various groups of xenobiotics.

  20. Global existence of solutions of a strongly coupled quasilinear parabolic system with applications to electrochemistry

    NASA Astrophysics Data System (ADS)

    Choi, Y. S.; Huan, Zhongdan; Lui, Roger

    2003-11-01

    This paper consists of two parts. In the first part, we proved the global existence of weak solutions of a strongly coupled quasilinear parabolic system in Rn using weak compactness method. In the second part, we considered the electrochemistry model studied in Choi and Lui (J. Differential Equations 116 (1995) 306) where the Poisson equation governing the electric potential is replaced by a local electro-neutrality condition. In one space dimension, the equations for the model is of the form considered in the first part of this paper except that the coefficient matrix is discontinuous at places where all the charged ions vanish. We approximate the equations by nicer operators and pass to the limit to obtain global existence of weak solutions. The non-negativity of weak solutions and L2-stability of the steady-state solutions are also shown under additional hypotheses.

  1. Structural properties and electrochemistry of α-LiFeO2

    NASA Astrophysics Data System (ADS)

    Abdel-Ghany, A. E.; Mauger, A.; Groult, H.; Zaghib, K.; Julien, C. M.

    2012-01-01

    In this work, we study the physico-chemistry and electrochemistry of lithium ferrite synthesized by solid-state reaction. Characterization included X-ray diffraction (XRD), scanning electronic microscopy (SEM), Raman scattering (RS), Fourier transform infrared spectroscopy (FTIR), and SQUID magnetometry. XRD peaks gradually sharpen with increasing firing temperature; all the diffraction peaks can be indexed to the cubic α-LiFeO2 phase (Fm3m space group) with the refined cell parameter a = 4.155 Å. RS and FTIR spectra show the vibrational modes due to covalent Fe-O bonds and the Li-cage mode at low-frequency. The electrochemical properties of Li/LiFeO2 are revisited along with the post-mortem analysis of the positive electrode material using XRD and Raman experiments.

  2. In-Depth Characterization of Protein Disulfide Bonds by Online Liquid Chromatography-Electrochemistry-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Switzar, Linda; Nicolardi, Simone; Rutten, Julie W.; Oberstein, Saskia A. J. Lesnik; Aartsma-Rus, Annemieke; van der Burgt, Yuri E. M.

    2016-01-01

    Disulfide bonds are an important class of protein post-translational modifications, yet this structurally crucial modification type is commonly overlooked in mass spectrometry (MS)-based proteomics approaches. Recently, the benefits of online electrochemistry-assisted reduction of protein S-S bonds prior to MS analysis were exemplified by successful characterization of disulfide bonds in peptides and small proteins. In the current study, we have combined liquid chromatography (LC) with electrochemistry (EC) and mass analysis by Fourier transform ion cyclotron resonance (FTICR) MS in an online LC-EC-MS platform to characterize protein disulfide bonds in a bottom-up proteomics workflow. A key advantage of a LC-based strategy is the use of the retention time in identifying both intra- and interpeptide disulfide bonds. This is demonstrated by performing two sequential analyses of a certain protein digest, once without and once with electrochemical reduction. In this way, the "parent" disulfide-linked peptide detected in the first run has a retention time-based correlation with the EC-reduced peptides detected in the second run, thus simplifying disulfide bond mapping. Using this platform, both inter- and intra-disulfide-linked peptides were characterized in two different proteins, ß-lactoglobulin and ribonuclease B. In order to prevent disulfide reshuffling during the digestion process, proteins were digested at a relatively low pH, using (a combination of) the high specificity proteases trypsin and Glu-C. With this approach, disulfide bonds in ß-lactoglobulin and ribonuclease B were comprehensively identified and localized, showing that online LC-EC-MS is a useful tool for the characterization of protein disulfide bonds.

  3. Studies of the electrochemistry of niobium(V) in sodium chloroaluminate and fluorochloroaluminate melts

    SciTech Connect

    Sienerth, K.D.

    1992-01-01

    Methods for the removal of oxide from LiF:NaF:KF (46.5:11.5:42.0 mole %) and sodium chloroaluminate molten salts were investigated. Raman spectroscopy of LiF:NaF:KF melts containing K[sub 2]TaF[sub 7] was utilized to determine the oxide level of the melts after several different purification techniques had been employed. In the case of sodium chloroaluminate, it was found that both phosgene (COCl[sub 2]) and carbon tetrachloride (CCl[sub 4]) were efficient oxide removal agents. The electrochemistry of Nb(V) in sodium chloroaluminate at 178[degrees]C was examined using various voltammetric techniques. It was found that reports of various workers in this system were erroneous due to the fact that these workers did not realize their melts were contaminated with oxide. The Nb(V) electrochemical behavior was re-investigated using melts that had been treated with either phosgene or carbon tetrachloride, and which were therefore essentially oxide-free. It was determined that Nb(V) first undergoes a one-electron reduction to Nb(IV), followed by further reduction of Nb(IV) to lower-oxidation state cluster species. Studies of the electrochemical behavior of Nb(V) were conducted in sodium chloroaluminate and fluorochloroaluminate melts, in the temperature range 160 to 500[degrees]C. While temperature had a marked effect on the electrochemistry of Nb(V), the addition of fluoride appeared to have little effect. Attempts to deposit niobium metal from these melts were somewhat successful.

  4. Probing the nature of electron transfer in metalloproteins on graphene-family materials as nanobiocatalytic scaffold using electrochemistry

    SciTech Connect

    Gupta, Sanju; Irihamye, Aline

    2015-03-15

    Graphene-based nanomaterials have shown great promise not only in nanoelectronics due to ultrahigh electron mobility but also as biocatalytic scaffolds owing to irreversible protein surface adsorption and facilitating direct electron transfer. In this work, we synthesized stable dispersions of graphene using liquid-phase exfoliation approach based on non-covalent interactions between graphene and 1-pyrenesulfonic acid sodium salt (Py–1SO{sub 3}), 1-pyrenemethylamine salt (Py − Me-NH{sub 2}) and Pluronic{sup ®} P-123 surfactant using only water as solvent compatible with biomolecules. The resulting graphene nanoplatelets (Gr-LPE) are characterized by a combination of analytical (microscopy and spectroscopy) techniques revealing mono- to few-layer graphene displaying that the exfoliation efficiency strongly depends upon the type of pyrene-based salts and organic surfactants. Moreover being completely water-based approach, we build robust nanoscaffolds of graphene-family nanomaterials (GFNs) namely, monolayer graphene, Gr-LPE (the one prepared with Pluronic{sup ®} P-123), graphene oxide (GO) and its reduced form (rGO) on glassy carbon electrode surface with three important metalloproteins include cytochrome c (Cyt c) [for electron transfer], myoglobin (Mb) [for oxygen storage] and horseradish peroxidase (HRP) [for catalyzing the biochemical reaction]. In order to demonstrate the nanobiocatalytical activity of these proteins, we used electrochemical interfacial direct electron transfer (DET) kinetics and attempt to determine the rate constant (k{sub ET}) using two different analytical approaches namely, linear sweep voltammetry and Laviron’s theory. We elucidated that all of the metalloproteins retain their structural integrity (secondary structure) upon forming mixtures with GFNs confirmed through optical and vibrational spectroscopy and biological activity using electrochemistry. Among the GFNs studied, Gr-LPE, GO and rGO support the efficient electrical

  5. Etude des chaines de spins par les methodes de la theorie quantique des champs

    NASA Astrophysics Data System (ADS)

    Allen, Dave

    Notre etude porte sur la chaine de spins en zigzag avec dimerisation dans le cas des spins 1/2 et 1. L'echelle de spin ordinaire et la chaine en zigzag simple en sont des cas particuliers. Dans la limite continue, ces systemes sont decrits par des modeles Wess-Zumino-Witten couples. Afin de pouvoir calculer les fonctions de correlation, nous exposons differentes equivalences quantiques permettant de simplifier les calculs. Dans le cas de chaines de spin 1/2, nous demontrons l'equivalence avec un modele de type Gross-Neveu, en fonction de fermions de Majorana; ces fermions decrivent alors les excitations elementaires du systeme. Nous exposons une vision classique de ces excitations afin de voir les mecanismes de confinement des spinons. Dans le cas de chaines de spin 1, l'etude est plus complexe. Nous pouvons decrire le systeme a l'aide de modeles sine-Gordon perturbes par de nombreuses interactions. En se limitant aux plus importantes, nous pouvons expliquer le comportement du gap en fonction du couplage interchaine observe numeriquement.

  6. L'etude de l'InP et du GaP suite a l'implantation ionique de Mn et a un recuit thermique

    NASA Astrophysics Data System (ADS)

    Bucsa, Ioan Gigel

    Cette these est dediee a l'etude des materiaux InMnP et GaMnP fabriques par implantation ionique et recuit thermique. Plus precisement nous avons investigue la possibilite de former par implantation ionique des materiaux homogenes (alliages) de InMnP et GaMnP contenant de 1 a 5 % atomiques de Mn qui seraient en etat ferromagnetique, pour des possibles applications dans la spintronique. Dans un premier chapitre introductif nous donnons les motivations de cette recherche et faisons une revue de la litterature sur ce sujet. Le deuxieme chapitre decrit les principes de l'implantation ionique, qui est la technique utilisee pour la fabrication des echantillons. Les effets de l'energie, fluence et direction du faisceau ionique sur le profil d'implantation et la formation des dommages seront mis en evidence. Aussi dans ce chapitre nous allons trouver des informations sur les substrats utilises pour l'implantation. Les techniques experimentales utilisees pour la caracterisation structurale, chimique et magnetique des echantillons, ainsi que leurs limitations sont presentees dans le troisieme chapitre. Quelques principes theoriques du magnetisme necessaires pour la comprehension des mesures magnetiques se retrouvent dans le chapitre 4. Le cinquieme chapitre est dedie a l'etude de la morphologie et des proprietes magnetiques des substrats utilises pour implantation et le sixieme chapitre, a l'etude des echantillons implantes au Mn sans avoir subi un recuit thermique. Notamment nous allons voir dans ce chapitre que l'implantation de Mn a plus que 1016 ions/cm 2 amorphise la partie implantee du materiau et le Mn implante se dispose en profondeur sur un profil gaussien. De point de vue magnetique les atomes implantes se trouvent dans un etat paramagnetique entre 5 et 300 K ayant le spin 5/2. Dans le chapitre 7 nous presentons les proprietes des echantillons recuits a basses temperatures. Nous allons voir que dans ces echantillons la couche implantee est polycristalline et les

  7. Humidity effect on nanoscale electrochemistry in solid silver ion conductors and the dual nature of its locality.

    PubMed

    Yang, Sang Mo; Strelcov, Evgheni; Paranthaman, M Parans; Tselev, Alexander; Noh, Tae Won; Kalinin, Sergei V

    2015-02-11

    Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically nonlocal cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor. We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and nonlocal) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.

  8. Humidity Effect on Nanoscale Electrochemistry in Solid Silver Ion Conductors and the Dual Nature of Its Locality

    SciTech Connect

    Yang, Sangmo; Strelcov, Evgheni; Paranthaman, Mariappan Parans; Tselev, Alexander; Noh, Tae Won; Kalinin, Sergei V.

    2015-01-07

    Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically non-local cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor. We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and non-local) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.

  9. Expedient preparation of nazlinine and a small library of indole alkaloids using flow electrochemistry as an enabling technology.

    PubMed

    Kabeshov, Mikhail A; Musio, Biagia; Murray, Philip R D; Browne, Duncan L; Ley, Steven V

    2014-09-05

    An expedient synthesis of the indole alkaloid nazlinine is reported. Judicious choice of flow electrochemistry as an enabling technology has permitted the rapid generation of a small library of unnatural relatives of this biologically active molecule. Furthermore, by conducting the key electrochemical Shono oxidation in a flow cell, the loading of electrolyte can be significantly reduced to 20 mol % while maintaining a stable, broadly applicable process.

  10. Electrochemistry for the Generation of Renewable Chemicals: One-Pot Electrochemical Deoxygenation of Xylose to δ-Valerolactone.

    PubMed

    James, Olusola O; Sauter, Waldemer; Schröder, Uwe

    2017-05-09

    In this study, the electrochemical conversion of xylose to δ-valerolactone via carbonyl intermediates is demonstrated. The conversion was achieved in aqueous media and at ambient conditions. This study also demonstrates that the feedstock for production of renewable chemicals and biofuels through electrochemistry can be extended to primary carbohydrate molecules. This is the first report on a one-pot electrochemical deoxygenation of xylose to δ-valerolactone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Electrochemistry in Near-Critical and Supercritical Fluids. 3. Studies of Br(-), I(-), and Hydroquinone in Aqueous Solutions.

    DTIC Science & Technology

    1986-02-01

    extraction of coal , 5 tar sands, 6 and biomass. 7 Complete oxidation cf most organic pollutants has also been achieved in a mixture of supercritical water...80-8169 136 ELECTROCHEMISTRY IN MERM-CRI TICAL AMD SUPERCRITICAL In1 FLUIDS I STUDIES OF 9.. (U) TEXAS UNIV AT AUSTIN DEPT OF CHENISTRY N M FLARSHEIM... Supercritical Fluids. 3. Studies of B and Hydroquinone in Aqueous Solutions By William M. Flarsheim*, Yu-Min Tsou*, Isacc Trachtenberg*, Keith P. Johnson

  12. Two New Sandwich-Type Manganese {Mn5}-Substituted Polyoxotungstates: Syntheses, Crystal Structures, Electrochemistry, and Magnetic Properties.

    PubMed

    Gupta, Rakesh; Khan, Imran; Hussain, Firasat; Bossoh, A Martin; Mbomekallé, Israël M; de Oliveira, Pedro; Sadakane, Masahiro; Kato, Chisato; Ichihashi, Katsuya; Inoue, Katsuya; Nishihara, Sadafumi

    2017-08-07

    Herein we report two pentanuclear Mn(II)-substituted sandwich-type polyoxotungstate complexes, [{Mn(bpy)}2Na(H2O)2(MnCl)2{Mn(H2O)}(AsW9O33)2](9-) and [{Mn(bpy)}2Na(H2O)2(MnCl){Mn(H2O)}2(SbW9O33)2](8-) (bpy = 2,2'-bipyridine), whose structures have been obtained by single-crystal X-ray diffraction (SCXRD), complemented by results obtained from elemental analysis, electrospray ionization mass spectrometry, Fourier transform infrared spectroscopy, and thermogravimetric analysis. They consist of two [B-α-XW9O33](9-) subunits sandwiching a cyclic assembly of the hexagonal [{Mn(bpy)}2Na(H2O)2(MnCl)2{Mn(H2O)}](9+) and [{Mn(bpy)}2Na(H2O)2(MnCl){Mn(H2O)}2](10+) moieties, respectively, and represent the first pentanuclear Mn(II)-substituted sandwich-type polyoxometalates (POMs). Both compounds have been synthesized by reacting MnCl2·4H2O with trilacunary Na9[XW9O33]·27H2O (X = As(III) and Sb(III)) POM precursors in the presence of bpy in a 1 M aqueous sodium chloride solution under mild reaction conditions. SCXRD showed that the alternate arrangement of three five-coordinated Mn(II) ions and two six-coordinated Mn(II) ions with an internal Na cation formed a coplanar six-membered ring that was sandwiched between two [B-α-XW9O33](9-) (X = As(III) and Sb(III)) subunits. The results of temperature-dependent direct-current (dc) magnetic susceptibility data indicated ferromagnetic interactions between Mn ions in the cluster. Moreover, alternating-current magnetic susceptibility measurements with a dc-biased magnetic field showed the existence of a ferromagnetic order for both samples. Electrochemistry studies revealed the presence of redox processes assigned to the Mn centers. They are associated with the deposition of material on the working electrode surface, possibly MnxOy, as demonstrated by electrochemical quartz crystal microbalance experiments.

  13. Conceptual design and experiments of electrochemistry-flushing technology for the remediation of historically Cr(Ⅵ)-contaminated soil.

    PubMed

    Li, Dong; Sun, Delin; Hu, Siyang; Hu, Jing; Yuan, Xingzhong

    2016-02-01

    A conceptual design and experiments, electrochemistry-flushing (E-flushing), using electrochemistry to enhance flushing efficiency for the remediation of Cr(Ⅵ)-contaminated soil is presented. The rector contained three compartments vertically superposed. The upper was airtight cathode compartment containing an iron-cathode. The middle was soil layer. The bottom was anode compartment containing an iron-anode and connected to a container by circulation pumps. H2 and OH(-) ions were produced at cathode. H2 increased the gas pressure in cathode compartment and drove flushing solution into soil layer forming flushing process. OH(-) ions entered into soil layer by eletromigration and hydraulic flow to enhance the desorption of Cr(Ⅵ). High potential gradient was applied to accelerate the electromigration of desorbed Cr(Ⅵ) ions and produced joule heat to increase soil temperature to enhance Cr(Ⅵ) desorption. In anode compartment, Fe(2+) ions produced at iron-anode reduced the desorbed Cr(Ⅵ) into Cr(3+) ions, which reacted with OH(-) ions forming Cr(OH)3. Experimental results show that Cr(Ⅵ) removal efficiency of E-flushing experiments was more than double of flushing experiments and reached the maximum of removal efficiency determined by desorption kinetics. All electrochemistry processes were positively used in E-flushing technology.

  14. Benefits of membrane electrodes in the electrochemistry of metalloproteins: mediated catalysis of Paracoccus pantotrophus cytochrome c peroxidase by horse cytochrome c: a case study.

    PubMed

    Paes de Sousa, P M; Pauleta, S R; Rodrigues, D; Simões Gonçalves, M L; Pettigrew, G W; Moura, I; Moura, J J G; Correia Dos Santos, M M

    2008-06-01

    A comparative study of direct and mediated electrochemistry of metalloproteins in bulk and membrane-entrapped solutions is presented. This work reports the first electrochemical study of the electron transfer between a bacterial cytochrome c peroxidase and horse heart cytochrome c. The mediated catalysis of the peroxidase was analysed both using the membrane electrode configuration and with all proteins in solution. An apparent Michaelis constant of 66 +/- 4 and 42 +/- 5 microM was determined at pH 7.0 and 0 M NaCl for membrane and bulk solutions, respectively. The data revealed that maximum activity occurs at 50 mM NaCl, pH 7.0, with intermolecular rate constants of (4.4 +/- 0.5) x 10(6) and (1.0 +/- 0.5) x 10(6) M(-1) s(-1) for membrane-entrapped and bulk solutions, respectively. The influence of parameters such as pH or ionic strength on the mediated catalytic activity was analysed using this approach, drawing attention to the fact that careful analysis of the results is needed to ensure that no artefacts are introduced by the use of the membrane configuration and/or promoters, and therefore the dependence truly reflects the influence of these parameters on the (mediated) catalysis. From the pH dependence, a pK of 7.5 was estimated for the mediated enzymatic catalysis.

  15. Analysis of the electrochemistry of hemes with Ems spanning 800 mV

    PubMed Central

    Zheng, Zhong; Gunner, M. R.

    2009-01-01

    The free energy of heme reduction in different proteins is found to vary over more than 18 kcal/mol. It is a challenge to determine how proteins manage to achieve this enormous range of Ems with a single type of redox cofactor. Proteins containing 141 unique hemes of a-, b-, and c-type, with bis-His, His-Met, and aquo-His ligation were calculated using Multi-Conformation Continuum Electrostatics (MCCE). The experimental Ems range over 800 mV from −350 mV in cytochrome c3 to 450 mV in cytochrome c peroxidase (vs. SHE). The quantitative analysis of the factors that modulate heme electrochemistry includes the interactions of the heme with its ligands, the solvent, the protein backbone, and sidechains. MCCE calculated Ems are in good agreement with measured values. Using no free parameters the slope of the line comparing calculated and experimental Ems is 0.73 (R2 = 0.90), showing the method accounts for 73% of the observed Em range. Adding a +160 mV correction to the His-Met c-type hemes yields a slope of 0.97 (R2 = 0.93). With the correction 65% of the hemes have an absolute error smaller than 60 mV and 92% are within 120 mV. The overview of heme proteins with known structures and Ems shows both the lowest and highest potential hemes are c-type, whereas the b-type hemes are found in the middle Em range. In solution, bis-His ligation lowers the Em by ≈205 mV relative to hemes with His-Met ligands. The bis-His, aquo-His, and His-Met ligated b-type hemes all cluster about Ems which are ≈200 mV more positive in protein than in water. In contrast, the low potential bis-His c-type hemes are shifted little from in solution, whereas the high potential His-Met c-type hemes are raised by ≈300 mV from solution. The analysis shows that no single type of interaction can be identified as the most important in setting heme electrochemistry in proteins. For example, the loss of solvation (reaction field) energy, which raises the Em, has been suggested to be a major factor in

  16. Electrochemistry and spectroscopy of electrolytes and cathode materials in room-temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Ryan, David Martin

    The demonstration of a stable, reversible, alkali metal anode is an important step in the development of practical secondary batteries using room temperature chloroaluminate molten salts as electrolytes. Such melts are made by mixing 1-ethyl-3-methylimidazolium chloride (EMIC) with aluminum chloride, and can be Lewis buffered by adding LiCl or NaCl. It has been shown previously that protons added to a sodium chloride buffered melt as 1-ethyl-3-methyfimidazolium hydrogen dichloride (EMIHCl2) provide a more negative voltage window and nearly reversible deposition-stripping behavior for sodium. It is reported here that triethanolamine hydrogen chloride is effective in widening the voltage window, allows the plating and stripping of both lithium and sodium, and is stable in buffered EMIC/AlCl3 melts for months. It is suggested that deprotonation of one ethanolic group of triethanolamine HCl is responsible for the effect. The electrochemistry and UV-visible spectroscopy of several vanadium oxides have been examined in room temperature melts. By varying the mole ratio of the two components, Lewis basic, neutral and acidic melts were made. Most oxides have very low solubility: V2O4 and V2O3 are insoluble and V2O5 has a solubility limit less than 5 mM, but the solubilities of the salts NaVO 3, Na3VO4, and NH4VO3, VOCl 3 and VOF3 are significantly higher. The electrochemistry of V2O5, NaVO3, Na3VO4, NH4VO3, VOCl3 and VOF3 is similar in neutral and acidic melts. In the neutral melt each compound shows an irreversible reduction at about 0.45V vs. an Al wire reference electrode. In an acidic melt (mole fraction AlCl3 = 0.55) each of these compounds exhibit additional reduction peaks at more positive potentials. Coulometric and spectroscopic data for the 0.45V reduction suggest that mixed oxidation state polyvanadates may be formed. Controlled potential coulometry demonstrated that the reduction at 0.45V was the reduction of V(V) to V(IV) and the more positive reduction peaks

  17. Overview of ICF program at Centre D{close_quote}Etudes de Limeil-Valenton

    SciTech Connect

    Cel-V Laser Team

    1996-05-01

    The major objectives of the CEA-DAM laser program is to determine the various requirements to achieve thermonuclear fusion in laboratory. We report here recent results obtained at Centre d{close_quote}Etudes de Limeil-Valenton on high density X-Ray implosions, radiative transfer processes, hydrodynamic instabilities and laser-plasma interaction involved in cavity physics. Ignition and a moderate gain appears to be achievable with a laser energy of about 1.5{minus}2 MJ delivered at {lambda}=0, 35 {mu}m with a shaped pulse (duration{approximately}16 ns). The construction of such a laser is realizable and a conceptual design is under preparation. {copyright} {ital 1996 American Institute of Physics.}

  18. Electrochemistry-based Approaches to Low Cost, High Sensitivity, Automated, Multiplexed Protein Immunoassays for Cancer Diagnostics

    PubMed Central

    Dixit, Chandra K.; Kadimisetty, Karteek; Otieno, Brunah A.; Tang, Chi; Malla, Spundana; Krause, Colleen E.; Rusling, James F.

    2015-01-01

    Early detection and reliable diagnostics are keys to effectively design cancer therapies with better prognoses. Simultaneous detection of panels of biomarker proteins holds great promise as a general tool for reliable cancer diagnostics. A major challenge in designing such a panel is to decide upon a coherent group of biomarkers which have higher specificity for a given type of cancer. The second big challenge is to develop test devices to measure these biomarkers quantitatively with high sensitivity and specificity, such that there are no interferences from the complex serum or tissue matrices. Lastly, integrating all these tests into a technology that doesn’t require exclusive training to operate, and can be used at point-of-care (POC) is another potential bottleneck in futuristic cancer diagnostics. In this article, we review electrochemistry-based tools and technologies developed and/or used in our laboratories to construct low-cost microfluidic protein arrays for highly sensitive detection of the panel of cancer-specific biomarkers with high specificity and at the same time have the potential to be translated into a POC. PMID:26525998

  19. Electrochemistry-based approaches to low cost, high sensitivity, automated, multiplexed protein immunoassays for cancer diagnostics.

    PubMed

    Dixit, Chandra K; Kadimisetty, Karteek; Otieno, Brunah A; Tang, Chi; Malla, Spundana; Krause, Colleen E; Rusling, James F

    2016-01-21

    Early detection and reliable diagnostics are keys to effectively design cancer therapies with better prognoses. The simultaneous detection of panels of biomarker proteins holds great promise as a general tool for reliable cancer diagnostics. A major challenge in designing such a panel is to decide upon a coherent group of biomarkers which have higher specificity for a given type of cancer. The second big challenge is to develop test devices to measure these biomarkers quantitatively with high sensitivity and specificity, such that there are no interferences from the complex serum or tissue matrices. Lastly, integrating all these tests into a technology that does not require exclusive training to operate, and can be used at point-of-care (POC) is another potential bottleneck in futuristic cancer diagnostics. In this article, we review electrochemistry-based tools and technologies developed and/or used in our laboratories to construct low-cost microfluidic protein arrays for the highly sensitive detection of a panel of cancer-specific biomarkers with high specificity which at the same time has the potential to be translated into POC applications.

  20. Reduced Graphene Oxide Thin Film on Conductive Substrates by Bipolar Electrochemistry

    PubMed Central

    Anis, Allagui; Mohammad, Ali Abdelkareem; Hussain, Alawadhi; Ahmed, S. Elwakil

    2016-01-01

    Recent years have shown an increased interest in developing manufacturing processes for graphene and its derivatives that consider the environmental impact and large scale cost-effectiveness. However, today’s most commonly used synthesis routes still suffer from their excessive use of harsh chemicals and/or the complexity and financial cost of the process. Furthermore, the subsequent transfer of the material onto a substrate makes the overall process even more intricate and time-consuming. Here we describe a single-step, single-cell preparation procedure of metal-supported reduced graphene oxide (rGO) using the principle of bipolar electrochemistry of graphite in deionized water. Under the effect of an electric field between two stainless steel feeder electrodes, grapheme layers at the anodic pole of the wireless graphite were oxidized into colloidal dispersion of GO, which migrated electrophoretically towards the anodic side of the cell, and deposited in the form of rGO (d(002) = 0.395 nm) by van der Waals forces. For substrates chemically more susceptible to the high anodic voltage, we show that the electrochemical setup can be adapted by placing the latter between the wireless graphite and the stainless steel feeder anode. This method is straightforward, inexpensive, environmentally-friendly, and could be easily scaled up for high yield and large area production of rGO thin films. PMID:26883173

  1. Dispersion of nanocrystalline Fe3O4 within composite electrodes: Insights on battery-related electrochemistry

    DOE PAGES

    David C. Bock; Takeuchi, Kenneth J.; Pelliccione, Christopher J.; ...

    2016-04-20

    Aggregation of nanosized materials in composite lithium-ion-battery electrodes can be a significant factor influencing electrochemical behavior. In this study, aggregation was controlled in magnetite, Fe3O4, composite electrodes via oleic acid capping and subsequent dispersion in a carbon black matrix. A heat treatment process was effective in the removal of the oleic acid capping agent while preserving a high degree of Fe3O4 dispersion. Electrochemical testing showed that Fe3O4 dispersion is initially beneficial in delivering a higher functional capacity, in agreement with continuum model simulations. However, increased capacity fade upon extended cycling was observed for the dispersed Fe3O4 composites relative to themore » aggregated Fe3O4 composites. X-ray absorption spectroscopy measurements of electrodes post cycling indicated that the dispersed Fe3O4 electrodes are more oxidized in the discharged state, consistent with reduced reversibility compared with the aggregated sample. Higher charge-transfer resistance for the dispersed sample after cycling suggests increased surface-film formation on the dispersed, high-surface-area nanocrystalline Fe3O4 compared to the aggregated materials. Furthermore, this study provides insight into the specific effects of aggregation on electrochemistry through a multiscale view of mechanisms for magnetite composite electrodes.« less

  2. Sites for catalysis and electrochemistry in solid oxide fuel cell (SOFC) anode

    NASA Astrophysics Data System (ADS)

    Rostrup-Nielsen, J. R.; Hansen, J. B.; Helveg, S.; Christiansen, N.; Jannasch, A.-K.

    2006-12-01

    Fuel cells represent a challenging overlap of catalysis and electrochemistry. This is illustrated by anode reactions in a solid oxide fuel cell. The sites for catalytic conversion of methane and electrochemical conversion of hydrogen on an SOFC anode appear not to be the same. The fuel (methane, hydrogen, etc.) is activated by chemisorption on the nickel surface of the anode. This is linked to the electrochemical reaction at the interface of the electrolyte and the nickel crystals converting oxygen ions into electrons and water by reactions with adsorbed hydrogen atoms resulting from the activation of the fuel. The sites for these reactions appear not to be the same. This is reflected by different sensitivities of the two steps to sulphur poisoning. The role of different sites on the nickel surface for the steam reforming reaction is well understood in terms of impact on activity for methane activation, carbon formation and sintering. The study is supplemented by an analysis of anodes having been exposed to 13000 of operation using a number of characterisation methods.

  3. Biomolecular detection at ssDNA-conjugated nanoparticles by nano-impact electrochemistry.

    PubMed

    Karimi, Anahita; Hayat, Akhtar; Andreescu, Silvana

    2017-01-15

    We describe the use of ssDNA functionalized silver nanoparticle (AgNP) probes for quantitative investigation of biorecognition and real time detection of biomolecular targets using nano-impact electrochemistry. The method is based on measurements of the individual collision events between ssDNA aptamer-functionalized AgNPs and a carbon fiber miroelectrode (CFME). Specific binding events of target analyte induced collision frequency changes enabling ultrasensitive detection of the aptamer target in a single step. These changes are assigned to the surface coverage of the NP by the ssDNA aptamers and subsequent conformational changes of the aptamer probe which affect the electron transfer between the NP and the electrode surface. The method enables sensitive and selective detection of ochratoxin A (OTA), chosen here as a model target, with a limit of detection of 0.05nM and a relative standard deviation of 4.9%. The study provides a means of characterizing bioconjugation of AgNPs with aptamers and assessing biomolecular recognition events with high sensitivity and without the use of exogenous reagents or enzyme amplification steps. This methodology can be broadly applicable to other bioconjugated systems, biosensing and related bioanalytical applications.

  4. Characterization of the roles of electrochemistry, convection and crack chemistry in stress corrosion cracking

    SciTech Connect

    Andresen, P.L.; Young, L.M.

    1995-12-31

    Understanding the role of ionic current flow within a crack and near the crack tip is fundamental to modeling of environmentally assisted crack advance. Critical conceptual issues and models related to ionic current flow within cracks, and the associated ``crevice`` chemistry and metal oxidation that results, are presented and examined in the light of experimental evidence. Various advanced techniques have been developed to evaluate the roles of electrochemistry, transport, and crack chemistry in stress corrosion cracking, with emphasis on high temperature ``pure`` water. These include high resolution crack length measurement by dc potential drop performed simultaneously with microsampling, electrochemical microprobe mapping, microinjection of species, and micropolarization of the crack. Conceptual issues addressed include the importance of the corrosion potential vs. oxidant concentration, the absence of oxidants and associated low corrosion potential within cracks, the location and role of macrocell currents associated with potential gradients from differential aeration cells, the localized nature of the microcell currents associated with dissolution at the crack tip, the importance of pH and adsorbed species on repassivation and crack advance, and the role of convection in crack chemistry and crack advance. Correct concepts are shown to be an essential pre-cursor to quantitative modeling.

  5. Tetramer model of leukoemeraldine-emeraldine electrochemistry in the presence of trihalogenoacetic acids. DFT approach.

    PubMed

    Barbosa, Nuno Almeida; Grzeszczuk, Maria; Wieczorek, Robert

    2015-01-15

    First results of the application of the DFT computational approach to the reversible electrochemistry of polyaniline are presented. A tetrameric chain was used as the simplest model of the polyaniline polymer species. The system under theoretical investigation involved six tetramer species, two electrons, and two protons, taking part in 14 elementary reactions. Moreover, the tetramer species were interacting with two trihalogenoacetic acid molecules. Trifluoroacetic, trichloroacetic, and tribromoacetic acids were found to impact the redox transformation of polyaniline as shown by cyclic voltammetry. The theoretical approach was considered as a powerful tool for investigating the main factors of importance for the experimental behavior. The DFT method provided molecular structures, interaction energies, and equilibrium energies of all of the tetramer-acid complexes. Differences between the energies of the isolated tetramer species and their complexes with acids are discussed in terms of the elementary reactions, that is, ionization potentials and electron affinities, equilibrium constants, electrode potentials, and reorganization energies. The DFT results indicate a high impact of the acid on the reorganization energy of a particular elementary electron-transfer reaction. The ECEC oxidation path was predicted by the calculations. The model of the reacting system must be extended to octamer species and/or dimeric oligomer species to better approximate the real polymer situation.

  6. Electrochemistry-assisted top-down characterization of disulfide-containing proteins.

    PubMed

    Zhang, Yun; Cui, Weidong; Zhang, Hao; Dewald, Howard D; Chen, Hao

    2012-04-17

    Covalent disulfide bond linkage in a protein represents an important challenge for mass spectrometry (MS)-based top-down protein structure analysis as it reduces the backbone cleavage efficiency for MS/MS dissociation. This study presents a strategy for solving this critical issue via integrating electrochemistry (EC) online with a top-down MS approach. In this approach, proteins undergo electrolytic reduction in an electrochemical cell to break disulfide bonds and then undergo online ionization into gaseous ions for analysis by electron-capture dissociation (ECD) and collision-induced dissociation (CID). The electrochemical reduction of proteins allows one to remove disulfide bond constraints and also leads to increased charge numbers of the resulting protein ions. As a result, sequence coverage was significantly enhanced, as exemplified by β-lactoglobulin A (24 vs 75 backbone cleavages before and after electrolytic reduction, respectively) and lysozyme (5 vs 66 backbone cleavages before and after electrolytic reduction, respectively). This methodology is fast and does not need chemical reductants, which would have an important impact in high-throughput proteomics research.

  7. Electrochemistry-Assisted Top-Down Characterization of Disulfide-Containing Proteins

    PubMed Central

    Zhang, Yun; Cui, Weidong; Zhang, Hao; Dewald, Howard D.; Chen, Hao

    2013-01-01

    Covalent disulfide bond linkage in a protein represents an important challenge for mass spectrometry (MS)-based top-down protein structure analysis as it reduces the backbone cleavage efficiency for MS/MS dissociation. This study presents a strategy for solving this critical issue via integrating electrochemistry (EC) online with top-down MS approach. In this approach, proteins undergo electrolytic reduction in an electrochemical cell to break disulfide bonds and then online ionized into gaseous ions for analysis by electron-capture dissociation (ECD) and collision-induced dissociation (CID). The electrochemical reduction of proteins allows to remove disulfide bond constraints and also leads to increased charge numbers of the resulting protein ions. As a result, sequence coverage was significantly enhanced, as exemplified by β-lactoglobulin A (24 vs. 73 backbone cleavages before and after electrolytic reduction, respectively) and lysozyme (5 vs. 66 backbone cleavages before and after electrolytic reduction, respectively). This methodology is fast and does not need chemical reductants, which would have an important impact in high-throughput proteomics research. PMID:22448817

  8. Simulation of the oxidative metabolism of diclofenac by electrochemistry/(liquid chromatography/)mass spectrometry.

    PubMed

    Faber, Helene; Melles, Daniel; Brauckmann, Christine; Wehe, Christoph Alexander; Wentker, Kristina; Karst, Uwe

    2012-04-01

    Diclofenac is a frequently prescribed drug for rheumatic diseases and muscle pain. In rare cases, it may be associated with a severe hepatotoxicity. In literature, it is discussed whether this toxicity is related to the oxidative phase I metabolism, resulting in electrophilic quinone imines, which can subsequently react with nucleophiles present in the liver in form of glutathione or proteins. In this work, electrochemistry coupled to mass spectrometry is used as a tool for the simulation of the oxidative pathway of diclofenac. Using this purely instrumental approach, diclofenac was oxidized in a thin layer cell equipped with a boron doped diamond working electrode. Sum formulae of generated oxidation products were calculated based on accurate mass measurements with deviations below 2 ppm. Quinone imines from diclofenac were detected using this approach. It could be shown for the first time that these quinone imines do not react with glutathione exclusively but also with larger molecules such as the model protein β-lactoglobulin A. A tryptic digest of the generated drug-protein adduct confirms that the protein is modified at the only free thiol-containing peptide. This simple and purely instrumental set-up offers the possibility of generating reactive metabolites of diclofenac and to assess their reactivity rapidly and easily.

  9. Water as a promoter and catalyst for dioxygen electrochemistry in aqueous and organic media.

    SciTech Connect

    Staszak-Jirkovsky, Jakub; Subbaraman, Ram; Strmcnik, Dusan; Harrison, Katherine L.; Diesendruck, Charles E.; Assary, Rajeev; Frank, Otakar; Kobr, Lukas; Wiberg, Gustav K.H; Genorio, Bostjan; Connell, Justin G.; Lopes, Pietro P.; Stamenkovic, Vojislav R.; Curtiss, Larry; Moore, Jeffrey S.; Zavadil, Kevin R.; Markovic, Nenad M.

    2015-11-01

    Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultradry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad center dot center dot center dot H2O (aqueous solutions) and LiO2 center dot center dot center dot H2O (organic solvents) complexes that place water in a configurationally favorable position for proton transfer to weakly adsorbed intermediates. We also find that, even at low concentrations (<10 ppm), water acts simultaneously as a promoter and as a catalyst in the production of Li2O2, regenerating itself through a sequence of steps that include the formation and recombination of H+ and OH-. We conclude that, although the binding energy between metal surfaces and oxygen intermediates is an important descriptor in electrocatalysis, understanding the role of water as a proton-donor reactant may explain many anomalous features in electrocatalysis at metal-liquid interfaces.

  10. Water as a promoter and catalyst for dioxygen electrochemistry in aqueous and organic media.

    DOE PAGES

    Staszak-Jirkovsky, Jakub; Subbaraman, Ram; Strmcnik, Dusan; ...

    2015-11-01

    Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultradry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad center dot center dot center dot H2O (aqueous solutions) and LiO2 center dot center dot center dot H2O (organic solvents) complexes that place water in a configurationally favorablemore » position for proton transfer to weakly adsorbed intermediates. We also find that, even at low concentrations (<10 ppm), water acts simultaneously as a promoter and as a catalyst in the production of Li2O2, regenerating itself through a sequence of steps that include the formation and recombination of H+ and OH-. We conclude that, although the binding energy between metal surfaces and oxygen intermediates is an important descriptor in electrocatalysis, understanding the role of water as a proton-donor reactant may explain many anomalous features in electrocatalysis at metal-liquid interfaces.« less

  11. Surface chemistry of bulk nanocrystalline pure iron and electrochemistry study in gas-flow physiological saline.

    PubMed

    Nie, F L; Zheng, Y F

    2012-07-01

    Conventional microcrystalline pure iron (MC-Fe) becomes a new candidate as biodegradable metals, which has the insufficient physical feature and inferior biodegradation behavior. Novel bulk nanocrystalline pure iron (NC-Fe) was fabricated via equal channel angular pressing technique in the present work to overcome these problems. The contact angle test with water and glycerol droplets shows a smaller angle (though >90°) of NC-Fe than that of MC-Fe, which implies a lower surface energy of NC-Fe. The surface roughness of NC-Fe increased greatly than that of MC-Fe. A further comparative study of corrosion and electrochemistry performance between NC-Fe and its original MC-Fe was investigated in physiological saline with different dissolved oxygen concentration, aiming to in vitro simulate the corrosion process of coronary stent occurred in physiological environment. The electrochemical impedance spectra analysis and anodic polarization measurements indicated that the NC-Fe exhibited higher corrosion resistance than that of the MC-Fe; meanwhile obvious enhanced corrosion resistance with the decrement of dissolved oxygen concentration was observed. Related equivalent circuit model and surface reconstruction process were further discussed, and the degradation mechanism of the MC-Fe and NC-Fe were finally established. Copyright © 2012 Wiley Periodicals, Inc.

  12. Reduced Graphene Oxide Thin Film on Conductive Substrates by Bipolar Electrochemistry

    NASA Astrophysics Data System (ADS)

    Anis, Allagui; Mohammad, Ali Abdelkareem; Hussain, Alawadhi; Ahmed, S. Elwakil

    2016-02-01

    Recent years have shown an increased interest in developing manufacturing processes for graphene and its derivatives that consider the environmental impact and large scale cost-effectiveness. However, today’s most commonly used synthesis routes still suffer from their excessive use of harsh chemicals and/or the complexity and financial cost of the process. Furthermore, the subsequent transfer of the material onto a substrate makes the overall process even more intricate and time-consuming. Here we describe a single-step, single-cell preparation procedure of metal-supported reduced graphene oxide (rGO) using the principle of bipolar electrochemistry of graphite in deionized water. Under the effect of an electric field between two stainless steel feeder electrodes, grapheme layers at the anodic pole of the wireless graphite were oxidized into colloidal dispersion of GO, which migrated electrophoretically towards the anodic side of the cell, and deposited in the form of rGO (d(002) = 0.395 nm) by van der Waals forces. For substrates chemically more susceptible to the high anodic voltage, we show that the electrochemical setup can be adapted by placing the latter between the wireless graphite and the stainless steel feeder anode. This method is straightforward, inexpensive, environmentally-friendly, and could be easily scaled up for high yield and large area production of rGO thin films.

  13. Electrohydrodynamic jet printing and a preliminary electrochemistry test of graphene micro-scale electrodes

    NASA Astrophysics Data System (ADS)

    Wang, Dazhi; Zha, Wen; Feng, Li; Ma, Qian; Liu, Xianming; Yang, Ning; Xu, Zheng; Zhao, Xiaojun; Liang, Junsheng; Ren, Tongqun; Wang, Xiaodong

    2016-04-01

    This paper reports the use of electrohydrodynamic jet (E-jet) printing technique for producing a wide range of graphene micro-scale structures. Ethyl cellulose-dispersed graphene ink and Nafion-dispersed graphene ink were prepared and used for E-Jet printing. A glass slide and PDMS substrate were used for E-Jet printing of graphene ink. The E-jet printed graphene micro-scale structures using ethyl cellulose-dispersed graphene ink presented a feature of center arrayed graphene surrounded by the track of evaporated solution. However, the E-Jet printed graphene structures using Nafion-dispersed graphene ink exhibited uniform arranged features. It was observed that the resistivity of the graphene structures printed from the ethyl cellulose-dispersed graphene ink was much lower than that from the Nafion-dispersed graphene ink. In addition, the graphene micro-scale electrodes were E-Jet printed for preliminary electrochemical applications. The results showed that the graphene micro-scale electrodes had a distinct response for the lead ion. Furthermore, a Pt/graphene composite electrode was formed and an electrochemistry test was conducted. It was found that the Pt /graphene composite electrode had a more sensitive response compared with the pure Pt electrode for electrochemical sensing.

  14. Forensic electrochemistry: indirect electrochemical sensing of the components of the new psychoactive substance "Synthacaine".

    PubMed

    Cumba, Loanda R; Kolliopoulos, Athanasios V; Smith, Jamie P; Thompson, Paul D; Evans, Peter R; Sutcliffe, Oliver B; do Carmo, Devaney R; Banks, Craig E

    2015-08-21

    "Synthacaine" is a New Psychoactive Substance which is, due to its inherent psychoactive properties, reported to imitate the effects of cocaine and is therefore consequently branded as "legal cocaine". The only analytical approach reported to date for the sensing of "Synthacaine" is mass spectrometry. In this paper, we explore and evaluate a range of potential analytical techniques for its quantification and potential use in the field screening "Synthacaine" using Raman spectroscopy, presumptive (colour) testing, High Performance Liquid Chromatography (HPLC) and electrochemistry. HPLC analysis of street samples reveals that "Synthacaine" comprises a mixture of methiopropamine (MPA) and 2-aminoindane (2-AI). Raman spectroscopy and presumptive (colour) tests, the Marquis, Mandelin, Simon's and Robadope test, are evaluated towards a potential in-the-field screening approach but are found to not be able to discriminate between the two when they are both present in the same sample, as is the case in the real street samples. We report for the first time a novel indirect electrochemical protocol for the sensing of MPA and 2-AI which is independently validated in street samples with HPLC. This novel electrochemical approach based upon one-shot disposable cost effective screen-printed graphite macroelectrodes holds potential for in-the-field screening for "Synthacaine".

  15. Electrochemistry-mass spectrometry for mechanistic studies and simulation of oxidation processes in the environment.

    PubMed

    Hoffmann, Th; Hofmann, D; Klumpp, E; Küppers, S

    2011-02-01

    Electrochemistry (EC) coupled to mass spectrometry (MS) has already been successfully applied to metabolism research for pharmaceutical applications, especially for the oxidation behaviour of drug substances. Xenobiotics (chemicals in the environment) also undergo various conversions; some of which are oxidative reactions. Therefore, EC-MS might be a suitable tool for the investigation of oxidative behaviour of xenobiotics. A further evaluation of this approach to environmental research is presented in the present paper using sulfonamide antibiotics. The results with sulfadiazine showed that EC-MS is a powerful tool for the elucidation of the oxidative degradation mechanism within a short time period. In addition, it was demonstrated that EC-MS can be used as a fast and easy method to model the chemical binding of xenobiotics to soil. The reaction of sulfadiazine with catechol, as a model substance for organic matter in soil, led to the expected chemical structure. Finally, by using EC-MS a first indication was obtained of the persistence of a component under chemical oxidation conditions for the comparison of the oxidative stability of different classes of xenobiotics. Overall, using just a few examples, the study demonstrates that EC-MS can be applied as a versatile tool for mechanistic studies of oxidative degradation pathways of xenobiotics and their possible interaction with soil organic matter as well as their oxidative stability in the environment. Further studies are needed to evaluate the full range of possibilities of the application of EC-MS in environmental research.

  16. Etudes Asymptotiques en Filtrage Non Lineaire Avec Petit Bruit D’Observation (Asymptotic Studies in Nonlinear Time Filtering with Small Observation Noise)

    DTIC Science & Technology

    1990-09-26

    titre de s DOCTEUR DE L’UNIVERSITE DE PROVENCE : SpdcialitM MATHEMATIQUES APPLIQUEES par PAULA M. L. P. MILHEIRO de OLIVEIRA Sujet de la these: ETUDES...PROVENCE Spdcialitd: MATHEMATIQUES APPLIQUEES par PAULA M. L. P. MILHEIRO de OLIVEIRA Sujet dela thse: E~TUDES ASYMPTOTIQUES EN FILTRAGE NON LINEAIRE...At Pk + h2 At p,]f6 2 ± h2 AtP] k CO lk + Ilk Donc C I~k+1 Pk1 (10) 1-iPk + C Cl Suivant un raisonnement par recurrence on trouve l’expression: Ilk_

  17. Horseradish peroxidase immobilization on carbon nanodots/CoFe layered double hydroxides: direct electrochemistry and hydrogen peroxide sensing.

    PubMed

    Wang, Yinling; Wang, Zhangcui; Rui, Yeping; Li, Maoguo

    2015-02-15

    Carbon nanodots and CoFe layered double hydroxide composites (C-Dots/LDHs) were prepared via simply mixing C-Dots and CoFe-LDHs. The as-prepared composites were used for the immobilization of horseradish peroxidase (HRP) on the glass carbon (GC) electrode. The electrochemical behavior of the HRP/C-Dots/LDHs/GC electrode and its application as a H2O2 biosensor were investigated. The results indicated that HRP immobilized by C-Dots/LDHs retained the activity of enzyme and displayed quasi-reversible redox behavior and fast electron transfer with an electron transfer rate constant ks of 8.46 s(-1). Under optimum experimental conditions, the HRP/C-Dots/LDHs/GC electrode displayed good electrocatalytic reduction activity and excellent analytic performance toward H2O2. The H2O2 biosensor showed a linear range of 0.1-23.1 μM (R(2) = 0.9942) with a calculated detection limit of 0.04 μM (S/N = 3). In addition, the biosensor exhibited high sensitivity, good selectivity, acceptable reproducibility and stability. The superior properties of this biosensor are attributed to the synergistic effect of HRP, C-Dots and CoFe-LDHs, which has been proved by investigating their electrochemical response to H2O2. Thus the C-Dots and LDHs composites provide a promising platform for the immobilization of redox enzymes and construction of sensitive biosensors.

  18. A highly efficient nano-cluster artificial peroxidase and its direct electrochemistry on a nano complex modified glassy carbon electrode.

    PubMed

    Hong, Jun; Wang, Wei; Huang, Kun; Yang, Wei-Yun; Zhao, Ying-Xue; Xiao, Bao-Lin; Gao, Yun-Fei; Moosavi-Movahedi, Zainab; Ghourchian, Hedayatollah; Moosavi-Movahedi, Ali Akbar

    2012-01-01

    A nano-cluster with highly efficient peroxide activity was constructed based on nafion (NF) and cytochrome c (Cyt c). UV-Vis spectrometry and transmission electron microscopy (TEM) methods were utilized for characterization of the nano-structured enzyme or artificial peroxidase (AP). The nano-cluster was composed of a Chain-Ball structure, with an average ball size of about 40 nm. The Michaelis-Menten (K(m)) and catalytic rate (k(cat)) constants of the AP were determined to be 2.5 ± 0.4 µM and 0.069 ± 0.001 s(-1), respectively, in 50 mM PBS at pH 7.0. The catalytic efficiency of the AP was evaluated to be 0.028 ± 0.005 µM(-1) s(-1), which was 39 ± 5% as efficient as the native horseradish peroxidase (HRP). The AP was also immobilized on a functional multi-wall carbon nanotube (MWNCTs)-gold colloid nanoparticles (AuNPs) nano-complex modified glassy carbon (GC) electrode. The cyclic voltammetry of AP on the nano complex modified GC electrode showed a pair of well-defined redox peaks with a formal potential (E°') of -45 ± 2 mV (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer rate constant (k(s)) was evaluated to be 0.65 s(-1). The surface concentration of electroactive AP on GC electrode (Γ) was 7 × 10(-10) mol cm(-2). The apparent Michaelis-Menten constant (K(m)(app)) was 0.23 nM.

  19. Self-assembled films of hemoglobin/laponite/chitosan: application for the direct electrochemistry and catalysis to hydrogen peroxide.

    PubMed

    Shan, Dan; Han, En; Xue, Huaiguo; Cosnier, Serge

    2007-10-01

    A highly stable biological film was formed on the functional glassy carbon electrode (GCE) via step-by-step self-assembly of chitosan (CHT), laponite, and hemoglobin (Hb). Cyclic voltammetry (CV) of the Hb/laponite/CHT/GCE showed a pair of stable and quasi-reversible peaks for the Hb-Fe(III)/Fe(II) redox couple at about -0.035 V versus a saturated calomel electrode in pH 6.0 phosphate buffer at a scan rate of 0.1 V s(-1). The electrochemical reaction of Hb entrapped on the laponite/CHT self-assembled film exhibited a surface-controlled electrode process. The formal potential of the Hb-heme-Fe(III)/Fe(II) couple varied linearly with the increase of pH over the range of 3.0-8.0 with a slope of -63 mV pH(-1), which implied that an electron transfer was accompanied by single-proton transfer in the electrochemical reaction. The position of the Soret absorption band of this self-assembled Hb/laponite/CHT film suggested that the entrapped Hb kept its secondary structure similar to its native state. The self-assembled film showed excellent long-term stability, the CV peak potentials kept in the same positions, and the cathodic peak currents retained 90% of their values after 60 days. The film was used as a biological catalyst to catalyze the reduction of hydrogen peroxide. The electrocatalytic response showed a linear dependence on the H2O2 concentration ranging widely from 6.2 x 10(-6) to 2.55 x 10(-3) M with a detection limit of 6.2 x 10(-6) M at 3 sigma.

  20. Direct electrochemistry of horseradish peroxidase immobilized on the layered calcium carbonate-gold nanoparticles inorganic hybrid composite.

    PubMed

    Li, Feng; Feng, Yan; Wang, Zhen; Yang, Limin; Zhuo, Linhai; Tang, Bo

    2010-06-15

    A mediator-free hydrogen peroxide (H(2)O(2)) biosensor was fabricated based on immobilization of horseradish peroxidase (HRP) on layered calcium carbonate-gold nanoparticles (CaCO(3)-AuNPs) inorganic hybrid composite. The proposed biosensor showed a strong electrocatalytic activity toward the reduction of H(2)O(2), which could be attributed to the favored orientation of HRP in the well-confined surface as well as the high electrical conductivity of the resulting CaCO(3)-AuNPs inorganic hybrid composite. The hybrid composite was obtained by the adsorption of AuNPs onto the surfaces of layered CaCO(3) through electrostatic interaction. The key analytical parameters relative to the biosensor performance such as pH and applied potential were optimized. The developed biosensor also exhibited a fast amperometric response (3s), a good linear response toward H(2)O(2) over a wide range of concentration from 5.0x10(-7) to 5.2x10(-3)M, and a low detection limit of 1.0x10(-7)M. The facile, inexpensive and reliable sensing platform based on layered CaCO(3)-AuNPs inorganic hybrid composite should hold a huge potential for the fabrication of more other biosensors.

  1. Enhanced direct electrochemistry of glucose oxidase and biosensing for glucose via synergy effect of graphene and CdS nanocrystals.

    PubMed

    Wang, Kun; Liu, Qian; Guan, Qing-Meng; Wu, Jun; Li, He-Nan; Yan, Jia-Jia

    2011-01-15

    Integrating graphene-based composites with enzyme provides a potent strategy to enhance biosensor performance due to their unique physicochemical properties. Herein we report on the utilization of graphene-CdS (G-CdS) nanocomposite as a novel immobilization matrix for the enzymes, which glucose oxidase (GOD) was chosen as model enzyme. In comparison with the graphene sheet and CdS nanocrystal, G-CdS nanocomposite exhibited excellent electron transfer properties for GOD with the rate constant (k(s)) of 5.9 s(-1) due to the synergy effect of graphene sheet and CdS nanocrystals. Further, based on the decrease of the electrocatalytic response of the reduced form of GOD to dissolved oxygen, the obtained glucose biosensor displays satisfactory analytical performance over an acceptable linear range from 2.0 to 16 mM with a detection limit of 0.7 mM, and also prevents the effects of interfering species, which is suitable for glucose determination by real samples. These results mean that this immobilization matrix not only can be used for immobilizing GOD, but also can be extended to other enzymes and bioactive molecules, thus providing a promising platform for the development of biosensors.

  2. Direct electrochemistry and electrochemical catalysis of myoglobin-TiO2 coated multiwalled carbon nanotubes modified electrode.

    PubMed

    Zhang, Lei; Tian, Dan-Bi; Zhu, Jun-Jie

    2008-11-01

    TiO(2) nanoparticles were homogeneously coated on multiwalled carbon nanotubes (MWCNTs) by hydrothermal deposition, and this nanocomposite might be a promising material for myoglobin (Mb) immobilization in view of its high biocompatibility and large surface. The glassy carbon (GC) electrode modified with Mb-TiO(2)/MWCNTs films exhibited a pair of well-defined, stable and nearly reversible cycle voltammetric peaks. The formal potential of Mb in TiO(2)/MWCNTs film was linearly varied in the range of pH 3-10 with a slope of 48.65 mV/pH, indicating that the electron transfer was accompanied by single proton transportation. The electron transfer between Mb and electrode surface, k(s) of 3.08 s(-1), was greatly facilitated in the TiO(2)/MWCNTs film. The electrocatalytic reductions of hydrogen peroxide were also studied, and the apparent Michaelis-Menten constant is calculated to be 83.10 microM, which shows a large catalytic activity of Mb in the TiO(2)/MWCNTs film to H(2)O(2). The modified GC electrode shows good analytical performance for amperometric determination of hydrogen peroxide. The resultant Mb-TiO(2)/MWCNTs modified glassy carbon electrode exhibited fast amperometric response to hydrogen peroxide reduction, long term life and excellent stability. Finally the activity of the sensor for nitric oxide reduction was also investigated.

  3. Direct electrochemistry and electrocatalytic activity of catalase immobilized onto electrodeposited nano-scale islands of nickel oxide.

    PubMed

    Salimi, Abdollah; Sharifi, Ensiyeh; Noorbakhsh, Abdollah; Soltanian, Saied

    2007-02-01

    Cyclic voltammetry was used for simultaneous formation and immobilization of nickel oxide nano-scale islands and catalase on glassy carbon electrode. Electrodeposited nickel oxide may be a promising material for enzyme immobilization owing to its high biocompatibility and large surface. The catalase films assembled on nickel oxide exhibited a pair of well defined, stable and nearly reversible CV peaks at about -0.05 V vs. SCE at pH 7, characteristic of the heme Fe (III)/Fe (II) redox couple. The formal potential of catalase in nickel oxide film were linearly varied in the range 1-12 with slope of 58.426 mV/pH, indicating that the electron transfer is accompanied by single proton transportation. The electron transfer between catalase and electrode surface, (k(s)) of 3.7(+/-0.1) s(-1) was greatly facilitated in the microenvironment of nickel oxide film. The electrocatalytic reduction of hydrogen peroxide at glassy carbon electrode modified with nickel oxide nano-scale islands and catalase enzyme has been studied. The embedded catalase in NiO nanoparticles showed excellent electrocatalytic activity toward hydrogen peroxide reduction. Also the modified rotating disk electrode shows good analytical performance for amperometric determination of hydrogen peroxide. The resultant catalase/nickel oxide modified glassy carbon electrodes exhibited fast amperometric response (within 2 s) to hydrogen peroxide reduction (with a linear range from 1 microM to 1 mM), excellent stability, long term life and good reproducibility. The apparent Michaelis-Menten constant is calculated to be 0.96(+/-0.05)mM, which shows a large catalytic activity of catalase in the nickel oxide film toward hydrogen peroxide. The excellent electrochemical reversibility of redox couple, high stability, technical simplicity, lake of need for mediators and short preparations times are advantages of this electrode. Finally the activity of biosensor for nitrite reduction was also investigated.

  4. Etude des phenomenes dynamiques ultrarapides et des caracteristiques impulsionnelles d'emission terahertz du supraconducteur YBCO

    NASA Astrophysics Data System (ADS)

    Savard, Stephane

    Les premieres etudes d'antennes a base de supraconducteurs a haute temperature critique emettant une impulsion electromagnetique dont le contenu en frequence se situe dans le domaine terahertz remontent a 1996. Une antenne supraconductrice est formee d'un micro-pont d'une couche mince supraconductrice sur lequel un courant continu est applique. Un faisceau laser dans le visible est focalise sur le micro-pont et place le supraconducteur dans un etat hors-equilibre ou des paires sont brisees. Grace a la relaxation des quasiparticules en surplus et eventuellement de la reformation des paires supraconductrices, nous pouvons etudier la nature de la supraconductivite. L'analyse de la cinetique temporelle du champ electromagnetique emis par une telle antenne terahertz supraconductrice s'est averee utile pour decrire qualitativement les caracteristiques de celle-ci en fonction des parametres d'operation tels que le courant applique, la temperature et la puissance d'excitation. La comprehension de l'etat hors-equilibre est la cle pour comprendre le fonctionnement des antennes terahertz supraconductrices a haute temperature critique. Dans le but de comprendre ultimement cet etat hors-equilibre, nous avions besoin d'une methode et d'un modele pour extraire de facon plus systematique les proprietes intrinseques du materiau qui compose l'antenne terahertz a partir des caracteristiques d'emission de celle-ci. Nous avons developpe une procedure pour calibrer le spectrometre dans le domaine temporel en utilisant des antennes terahertz de GaAs bombarde aux protons H+ comme emetteur et detecteur. Une fois le montage calibre, nous y avons insere une antenne emettrice dipolaire de YBa 2Cu3O7-delta . Un modele avec des fonctions exponentielles de montee et de descente du signal est utilise pour lisser le spectre du champ electromagnetique de l'antenne de YBa 2Cu3O7-delta, ce qui nous permet d'extraire les proprietes intrinseques de ce dernier. Pour confirmer la validite du modele

  5. Inherent electrochemistry and activation of chemically modified graphenes for electrochemical applications.

    PubMed

    Moo, James Guo Sheng; Ambrosi, Adriano; Bonanni, Alessandra; Pumera, Martin

    2012-04-01

    Graphene research is currently at the frontier of electrochemistry. Many different graphene-based materials are employed by electrochemists as electrodes in sensing and in energy-storage devices. Because the methods for their preparation are inherently different, graphene materials are expected to exhibit different electrochemical behaviors depending on the functionalities and density of defects present. Electrochemical treatment of these "chemically modified graphenes" (CMGs) represents an easy approach to alter surface functionalities and consequently tune the electrochemical performance. Herein, we report a preliminary electrochemical characterization of four common chemically modified graphenes, namely: graphene oxide, graphite oxide, chemically reduced graphene oxide, and thermally reduced graphene oxide. These CMGs were compared with graphite as a reference material. Cyclic voltammetry was used to ascertain the chemical functionalities present and to understand the potential ranges in which the materials were electroactive. Electrochemical treatment with either an oxidative or a reductive fixed potential were then carried out to activate these chemically modified graphenes. The effects of such electrochemical treatments on their electrocatalytic properties were then investigated by cyclic voltammetry in the presence of well-known redox probes, such as [Fe(CN)(6)](4-/3-), Fe(3+/2+), [Ru(NH(3))(6)](2+/3+), and ascorbic acid. Thermally reduced graphene oxide exhibited the best electrochemical behavior amongst all of the CMGs, with the fastest rate of heterogeneous electron transfer (HET) and the lowest overpotentials. These findings will have far-reaching consequences for the evaluation of different CMGs as electrode materials in electrochemical devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The Investigation and Characterization of the Group 3 [Nickel-Iron]-Hydrogenases Using Protein Film Electrochemistry

    NASA Astrophysics Data System (ADS)

    McIntosh, Chelsea Lee

    Hydrogenases, the enzymes that reversibly convert protons and electrons to hydrogen, are used in all three domains of life. [NiFe]-hydrogenases are considered best suited for biotechnological applications because of their reversible inactivation with oxygen. Phylogenetically, there are four groups of [NiFe]-hydrogenases. The best characterized group, "uptake" hydrogenases, are membrane-bound and catalyze hydrogen oxidation in vivo. In contrast, the group 3 [NiFe]-hydrogenases are heteromultimeric, bifunctional enzymes that fulfill various cellular roles. In this dissertation, protein film electrochemistry (PFE) is used to characterize the catalytic properties of two group 3 [NiFe]-hydrogenases: HoxEFUYH from Synechocystsis sp. PCC 6803 and SHI from Pyrococcus furiosus. First, HoxEFUYH is shown to be biased towards hydrogen production. Upon exposure to oxygen, HoxEFUYH inactivates to two states, both of which can be reactivated on the timescale of seconds. Second, we show that PfSHI is the first example of an oxygen tolerant [NiFe]-hydrogenase that produces two inactive states upon exposure to oxygen. Both inactive states are analogous to those characterized for HoxEFUYH, but oxygen exposed PfSHI produces a greater fraction that reactivates at high potentials, enabling hydrogen oxidation in the presence of oxygen. Third, it is shown that removing the NAD(P)-reducing subunits from PfSHI leads to a decrease in bias towards hydrogen oxidation and renders the enzyme oxygen sensitive. Both traits are likely due to impaired intramolecular electron transfer. Mechanistic hypotheseses for these functional differences are considered.

  7. Semiconductor electrochemistry of coal pyrite. Final technical report, September 1990--September 1995

    SciTech Connect

    Osseo-Asare, K.; Wei, Dawei

    1996-01-01

    This project seeks to advance the fundamental understanding of the physico-chemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. Central to this research is the use of synthetic microsize particles of pyrite as model microelectrodes to investigate the semiconductor electrochemistry of pyrite. The research focuses on: (a) the synthesis of microsize particles of pyrite in aqueous solution at room temperature, (b) the formation of iron sulfide complex, the precursor of FeS or FeS{sub 2}, and (c) the relationship between the semiconductor properties of pyrite and its interfacial electrochemical behavior in the dissolution process. In Chapter 2, 3 and 4, a suitable protocol for preparing microsize particles of pyrite in aqueous solution is given, and the essential roles of the precursors elemental sulfur and ``FeS`` in pyrite formation are investigated. In Chapter 5, the formation of iron sulfide complex prior to the precipitation of FeS or FeS{sub 2} is investigated using a fast kinetics technique based on a stopped-flow spectrophotometer. The stoichiometry of the iron sulfide complex is determined, and the rate and formation constants are also evaluated. Chapter 6 provides a summary of the semiconductor properties of pyrite relevant to the present study. In Chapters 7 and 8, the effects of the semiconductor properties on pyrite dissolution are investigated experimentally and the mechanism of pyrite dissolution in acidic aqueous solution is examined. Finally, a summary of the conclusions from this study and suggestions for future research are presented in Chapter 9.

  8. The significant role of carboxylated carbonaceous fragments in the electrochemistry of carbon nanotubes.

    PubMed

    Ma, Xiao; Jia, Li; Zhang, Lu; Zhu, Liande

    2014-04-01

    Carbon nanotubes (CNTs) have been widely employed as electrode materials in diverse branches of electrochemistry, which are claimed to display dramatically improved electrochemical behaviour compared to the conventional carbon materials. But a series of recent publications have demonstrated that the electrocatalysis of CNTs might be due to the presence of some impurities, such as metallic catalysts, nanographitic particles and amorphous carbon. For this reason, CNTs are usually purified or treated with nitric acid or nitric and sulphuric acid prior to their versatile applications. However, the strong acidic and oxidative conditions are so aggressive that serious erosion of the tube structures has inevitably taken place, which creates defects on the sidewalls and gives rise to numerous molecular byproducts, commonly referred as carboxylated carbonaceous fragments (CCFs). The adsorption of CCFs on CNTs greatly alters the surface conditions of CNTs which may significantly impact on their electrochemical properties. To this end, we wish to disclose whether the electrocatalysis of the nitric acid purified CNTs is affected by the adsorption of the CCFs. Ascorbic acid (AA) and β-nicotinamide adenine dinucleotide (NADH) as selected as the targeting benchmarks that are known to be insensitive to the presence of metallic impurities, which may guarantee the preclusion of the promoting contributions from the metallic catalysts resident in CNTs. We have demonstrated that the electrocatalytic activities of the CNTs are actually dominated by the adsorbed CCFs generated during the acidic pre-treatment. After removal of the CCFs by base rinse, the electrocatalytic properties of CNTs are greatly deteriorated and degraded to the level similar to the conventional graphite powder. We believe this finding is particularly meaningful to uncover the mysterious electrocatalysis of CNTs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Synthesis, Electrochemistry and Electrogenerated Chemiluminesce of two BODIPY-Appended Bipyridine Homologues

    PubMed Central

    Qi, Honglan; Teesdale, Justin J.; Pupillo, Rachel C.

    2014-01-01

    Two new 2,2’-bipyridine (bpy) derivatives containing ancillary BODIPY chromophores attached at the 5- and 5’-positions (BB3) or 6- and 6’-positions (BB4) were prepared and characterized. In this work, the basic photophysics, electrochemistry and electrogenerated chemiluminescence (ECL) of BB3 and BB4 are compared with those previously reported for a related bpy-BODIPY derivative (BB2) (J. Phys. Chem. C 2011, 115, 17993–18001). Cyclic voltammetry revealed that BB3 and BB4 display reversible 2e− oxidation and reduction waves, which consist of two closely spaced (50 – 70 mV) 1e− events. This redox behavior is consistent with the frontier molecular orbitals calculated for BB3 and BB4 and indicates that the 2,2’-bipyridine spacer of each bpy- BODIPY homologue does not facilitate efficient electronic communication between the tethered indacene units. In the presence of a coreactant such as tri-n-propylamine (TPA) or benzoyl peroxide (BPO), BB3 and BB4 exhibit strong ECL and produce spectra that are very similar to their corresponding photoluminescence profiles. The ECL signal obtained under annihilation conditions, however, is significantly different and is characterized by two distinct bands. One of these bands is centered at ~570 nm and is attributed to emission via an S- or T-route. The second band, occurs at longer wavelengths and is centered around ~740 nm. The shape and concentration dependence of this long-wavelength ECL signal is not indicative of emission from an excimer or aggregate, but rather is suggests that a new emissive species is formed from the bpy-BODIPY luminophores during the annihilation process. PMID:23980850

  10. Integration of Electrochemistry with Ultra Performance Liquid Chromatography/Mass Spectrometry (UPLC/MS)

    PubMed Central

    Cai, Yi; Zheng, Qiuling; Liu, Yong; Helmy, Roy; Loo, Joseph A.; Chen, Hao

    2015-01-01

    This study presents the development of ultra-performance liquid chromatography/mass spectrometry (UPLC/MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of disulfide bond-containing proteins/peptides. In our approach, a protein/peptide mixture sample undergoes fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and MS/MS analyses. The electrochemical cell is coupled to MS using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, disulfide bond-containing peptides can be differentiated from those without disulfide bonds as the former are electroactive and reducible. Tandem MS analysis of the disulfide-reduced peptide ions provides increased sequence and disulfide linkage pattern information. In a reactive DESI-MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which would be useful in top-down protein structure analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1~2 orders of magnitude by using UPLC for the LC/EC/MS platform, in comparison to the previously used high performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis. PMID:26307715

  11. Endogenous minerals have influences on surface electrochemistry and ion exchange properties of biochar.

    PubMed

    Zhao, Ling; Cao, Xinde; Zheng, Wei; Wang, Qun; Yang, Fan

    2015-10-01

    The feedstocks for biochar production are diverse and many of them contain various minerals in addition to being rich in carbon. Twelve types of biomass classified into 2 categories: plant-based and municipal waste, were employed to produce biochars under 350 °C and 500 °C. Their pH, point of zero net charge (PZNC), zeta potential, cation and anion exchange capacity (CEC and AEC) were analyzed. The municipal waste-based biochars (MW-BC) had higher mineral levels than the plant-based biochars (PB-BC). However, the water soluble mineral levels were lower in the MW-BCs due to the dominant presence of less soluble minerals, such as CaCO3 and (Ca,Mg)3(PO4)2. The higher total minerals in MW-BCs accounted for the higher PZNC (5.47-9.95) than in PB-BCs (1.91-8.18), though the PZNCs of the PB-BCs increased more than that of the MW-BCs as the production temperature rose. The minerals had influence on the zeta potentials via affecting the negative charges of biochars and the ionic strength of solution. The organic functional groups in PB-BCs such as -COOH and -OH had a greater effect on the CEC and AEC, while the minerals had a greater effect on that of MW-BCs. The measured CEC and AEC values had a strong positive correlation with the total amount of soluble cations and anions, respectively. Results indicated that biochar surface charges depend not only on the organic functional groups, but also on the minerals present and to some extent, minerals have more influences on the surface electrochemistry and ion exchange properties of biochar.

  12. Structural evolution and electrochemistry of monoclinic NaNiO2 upon the first cycling process

    NASA Astrophysics Data System (ADS)

    Han, Man Huon; Gonzalo, Elena; Casas-Cabanas, Montse; Rojo, Teófilo

    2014-07-01

    Electrochemistry and structural evolution of monoclinic NaNiO2 as a cathode material for Na-ion battery is reported. The initial charge capacity reached 160 mA h g-1 and the following discharge capacity of 114.6 mA h g-1, within the voltage range of 4.0-1.5 V at C/10. The multiple phase transition leading to O‧3, P‧3, P″3, O″3, and O‴3 stacking types (NaNiO2, Na0.91NiO2, Na0.84NiO2, Na0.81NiO2 and Na0.79NiO2 transitions, respectively, according to a previous report) during the 1st charge/discharge process is analysed using ex situ and in situ XRD techniques, and the stoichiometry of each phase is herein revised. The charge/discharge profile shows a highly reversible nature of the cathode, except that fully sodiated phase could not be achieved at the subsequent discharge. Two new phases have been discovered: a monoclinic O3 structure (designated as O⁗3) at the beginning of the charge (and end of discharge) and a P3 structure (designated as P‴3) at 3.38 V that appeared only during the charge process. The composition of the new O⁗3-phase corresponds to Na0.83NiO2, which is the closest to the fully sodiated phase at room temperature achieved during the discharge process reported up to date, and the composition of the new P‴3-phase corresponds approximately to Na0.50NiO2.

  13. [Preliminary research on a new method of NO3- -N wastewater treatment based on electrochemistry].

    PubMed

    Ye, Shu-fan; Hu, Xiao-min; Zhang, Yang; Dong, Jun

    2010-08-01

    A new method based on electrochemistry was presented to treat NO3- -N wastewater by analyzing theories of Pd-Me bimetal catalytic reduction of NO3- -N and NH4+ -N break point chlorination process. Presented method mainly includes following characteristics. Firstly, NO3- -N can be catalytically reduced in electric field while Ti substrate cathode was modified by common metallic elements which have empty electronic track. Secondly, NO3- -N reduction product can be controlled mainly is NH4+ -N by adjusting ratio of catalytic elements and electrolysis conditions. Finally, NH4+ -N is oxidized to harmless product N2-N by HOCl which produced from Cl- by anode oxidation process. Experiments were carried out to verified upwards theoretical assumptions. It's indicated that cathode modified by metal elements of Co and Cu can catalytic reduce NO3- -N in simulated wastewater effectively, as well as reduction product mainly was NH4+ -N while the molar ratio of Co and Cu in cathode precursor solution was 1:1. If Cl- was added to electrolysis system, NH4+ -N produced from NO3- -N reduction could be oxidized to N2-N by the anode action. Under the conditions of plate distance of 6mm, electric current of 400 mA and electrolysis time of 2.5 h, the concentration of NO3- -N, NO2- -N, NH4+ -N, and TN of simulated wastewater which initially contain 100 mg/L NO3- -N and 1000 mg/L Cl- decreased to 2.9 mg/L, 0.5 mg/L, 1.7 mg/L and 6.0 mg/L respectively.

  14. Electrochemically modulated liquid chromatography: Theoretical investigations and applications from the perspectives of chromatography and interfacial electrochemistry

    SciTech Connect

    Keller, David W.

    2005-01-01

    Electrochemically modulated liquid chromatography (EMLC) employs a conductive material as both a stationary phase for chromatographic separations and as a working electrode for performing electrochemistry experiments. This dual functionality gives EMLC the capacity to manipulate chromatographic separations by changing the potential applied (Eapp) to the stationary phase with respect to an external reference. The ability to monitor retention as a function of Eapp provides a means to chromatographically monitor electrosorption processes at solid-liquid interfaces. In this dissertation, the retention mechanism for EMLC is examined from the perspective of electrical double layer theory and interfacial thermodynamics. From the chromatographic data, it is possible to determine the interfacial excess (Λ) of a solute and changes in interfacial tension (dγ) as a function of both Eapp and the supporting electrolyte concentration. Taken together, these two experimentally manipulated parameters can be examined within the context of the Gibbs adsorption equation to delineate the contribution of a variety of interfacial properties, including the charge of solute on the stationary phase and the potential of zero charge (PZC), to the mechanism behind EMLC-based retention. The chromatographic probing of interfacial phenomena is complemented by electroanalytical experiments that exploit the ability to monitor the electronic current flowing through an EMLC column. Cyclic voltammetry and chronoamperometry of an EMLC column are used to determine the electronic performance characteristics of an EMLC column. An electrochemical flow injection analysis of a column is provided in which the current required to maintain a constant Eapp is monitored and provides a way to examine the influence that acetonitrile and supporting electrolyte composition, flow rate, column backpressure, and ionic strength have on the structure of electrified interfaces.

  15. Semiconductor electrochemistry of coal pyrite. Technical progress report, April--June 1992

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1992-12-01

    Pyrite synthesis is of interest in many diverse fields, such as geology, fuel processing technology, chemistry, metallurgy, materials science, and so on. Based on fundamental studies of this process, the formation mechanisms of this important sulfide on the earth can be better understood. The studies can also help us to better understand the surface chemistry and electrochemistry of pyrite, thereby assisting in the development of more efficient processes for removal of the sulfide from coal. The work performed during this quarter focuses on the study of the reaction between aqueous sulfide ions and dissolved Fe(II) salts by using a stopped-flow spectrophotometric technique. At a wavelength of 500 mn, no absorption was observed with either aqueous sulfide or dissolved Fe(II) salt alone. However, when the two solutions were mixed, a strong absorbance appeared at the same wavelength. The absorbance-time curve showed that a black material formed at the first few seconds of the reaction, then this material decayed and changed gradually to a lighter dark material within the following several minutes. These processes were pH-dependent. It was more likely to form the black intermediate at the pH range from 7 to 8. This indicates that the reaction between Fe{sup 2+} and HS{sup {minus}} results in the formation of the black intermediate because in this pH range, both Fe{sup 2+} and HS{sup {minus}} are the predominant species. The absorbance varied linearly with the concentration of the reactant for the first step of the reaction. The absorptivity of the black intermediate was determined as 4800 l/mol/cm. By means of this spectrophotometric technique, the stoichiometry, the equilibrium constant and the rate constant of the reaction will be determined.

  16. Immobilization of alkynyl functionalized manganese phthalocyanine via click electrochemistry for electrocatalytic oxygen evolution reaction.

    PubMed

    Öztaş, B; Akyüz, D; Koca, A

    2017-10-04

    Peripherally and non-peripherally terminal alkynyl substituted manganese phthalocyanines (MnPc) were synthesized and characterized and then used as functional materials in modified electrodes. MnPcs were substituted with alkynyl groups, which are reactive moieties in click electrochemistry (CEC) reactions. Mn(iii) cations were incorporated into the cavity of the Pc ring in order to increase the redox activity of the complexes. Electrochemical characterizations of the complexes were determined by voltammetric and in situ spectroelectrochemical measurements in order to determine their possible technological applications. MnPc complexes illustrated five redox couples and these redox couples were assigned as [Cl-Mn(III)Pc(2-)]/[Cl-Mn(II)Pc(2-)](1-), [Cl-Mn(II)Pc(2-)](1-)/[Cl-Mn(I)Pc(2-)](2-), [Cl-Mn(I)Pc(2-)](2-)/[ Cl-Mn(I)Pc(3-)](3-), and [Cl-Mn(III)Pc(2-)]/[Cl-Mn(III)Pc(1-)](1+) redox processes. The position of the substituents affected the mechanism of the redox reactions and influenced the tendency to react with the molecular oxygen. Moreover, changing the position of the substituents slightly influenced the peak potentials and reversibility of the redox processes. For the applications, modified electrodes (ITO/PANI-N3-MnPc and GCE/PANI-N3-MnPc) were constructed with CEC reaction between azido functionalized polyaniline (PANI-N3) and terminally alkynyl substituted MnPcs and these electrodes. Voltammetric characterizations of the modified electrodes illustrated suitable redox activity and conductivity for the practical applications. Finally, the GCE/PANI-N3-MnPc electrode was tested as a potential electrocatalyst for water splitting reaction. Although the GCE/PANI-N3-MnPc electrode did not catalyze the hydrogen evolution reaction (HER), it significantly catalyzed the oxygen evolution reaction (OER) in aqueous solution.

  17. Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries

    DOE PAGES

    Lin, Feng; Liu, Yijin; Yu, Xiqian; ...

    2017-08-30

    Rechargeable battery technologies have ignited major breakthroughs in contemporary society, including but not limited to revolutions in transportation, electronics, and grid energy storage. The remarkable development of rechargeable batteries is largely attributed to in-depth efforts to improve battery electrode and electrolyte materials. There are, however, still intimidating challenges of lower cost, longer cycle and calendar life, higher energy density, and better safety for large scale energy storage and vehicular applications. Further progress with rechargeable batteries may require new chemistries (lithium ion batteries and beyond) and better understanding of materials electrochemistry in the various battery technologies. In the past decade, advancementmore » of battery materials has been complemented by new analytical techniques that are capable of probing battery chemistries at various length and time scales. Synchrotron X-ray techniques stand out as one of the most effective methods that allows for nearly nondestructive probing of materials characteristics such as electronic and geometric structures with various depth sensitivities through spectroscopy, scattering, and imaging capabilities. This article begins with the discussion of various rechargeable batteries and associated important scientific questions in the field, followed by a review of synchrotron X-ray based analytical tools (scattering, spectroscopy and imaging) and their successful applications (ex situ, in situ, and in operando) in gaining fundamental insights into these scientific questions. Furthermore, electron microscopy and spectroscopy complement the detection length scales of synchrotron X-ray tools, and are also discussed towards the end. We highlight the importance of studying battery materials by combining analytical techniques with complementary length sensitivities, such as the combination of X-ray absorption spectroscopy and electron spectroscopy with spatial resolution

  18. Recent Advances in Modeling Transition Metal Oxides for Photo-electrochemistry

    NASA Astrophysics Data System (ADS)

    Caspary Toroker, Maytal

    Computational research offers a wide range of opportunities for materials science and engineering, especially in the energy arena where there is a need for understanding how material composition and structure control energy conversion, and for designing materials that could improve conversion efficiency. Potential inexpensive materials for energy conversion devices are metal oxides. However, their conversion efficiency is limited by at least one of several factors: a too large band gap for efficiently absorbing solar energy, similar conduction and valence band edge characters that may lead to unfavorably high electron-hole recombination rates, a valence band edge that is not positioned well for oxidizing water, low stability, low electronic conductivity, and low surface reactivity. I will show how we model metal oxides with ab-initio methods, primarily DFT +U. Our previous results show that doping with lithium, sodium, or hydrogen could improve iron (II) oxide's electronic properties, and alloying with zinc or nickel could improve iron (II) oxide's optical properties. Furthermore, doping nickel (II) oxide with lithium could improve several key properties including solar energy absorption. In this talk I will highlight new results on our understanding of the mechanism of iron (III) oxide's surface reactivity. Our theoretical insights bring us a step closer towards understanding how to design better materials for photo-electrochemistry. References: 1. O. Neufeld and M. Caspary Toroker, ``Pt-doped Fe2O3 for enhanced water splitting efficiency: a DFT +U study'', J. Phys. Chem. C 119, 5836 (2015). 2. M. Caspary Toroker, ``Theoretical Insights into the Mechanism of Water Oxidation on Non-stoichiometric and Ti - doped Fe2O3 (0001)'', J. Phys. Chem. C, 118, 23162 (2014). This research was supported by the Morantz Energy Research Fund, the Nancy and Stephen Grand Technion Energy Program, the I-CORE Program of the Planning and Budgeting Committee, and The Israel Science

  19. Integrating bipolar electrochemistry and electrochemiluminescence imaging with microdroplets for chemical analysis.

    PubMed

    Wu, Suozhu; Zhou, Zhenyu; Xu, Linru; Su, Bin; Fang, Qun

    2014-03-15

    Here we develop a microdroplet sensor based on bipolar electrochemistry and electrochemiluminescence (ECL) imaging. The sensor was constructed with a closed bipolar cell on a hybrid poly(dimethylsioxane) (PDMS)-indium tin oxide (ITO) glass microchip. The ITO microband functions as the bipolar electrode and its two poles are placed in two spatially separate micro-reservoirs predrilled on the PDMS cover. After loading microliter-sized liquid droplets of tris(2,2'-bipyridyl) ruthenium (II)/2-(dibutylamino) ethanol (Ru(bpy)3(2+)/DBAE) and the analyte to the micro-reservoirs, an appropriate external voltage imposed on the driving electrodes could induce the oxidation of Ru(bpy)3(2+)/DBAE and simultaneous reduction of the analyte at the anodic and cathodic poles, respectively. ECL images generated by Ru(bpy)3(2+)/DBAE oxidation at the anodic pole and the electrical current flowing through the bipolar electrode can be recorded for quantitative analyte detection. Several types of quinones were selected as model analytes to demonstrate the sensor performance. Furthermore, the cathodic pole of bipolar electrode can be modified with (3-aminopropyl)triethoxysilane-gold nanoparticles-horseradish peroxidase composites for hydrogen peroxide detection. This microdroplet sensor with a closed bipolar cell can avoid the interference and cross-contamination between analyte solutions and ECL reporting reagents. It is also well adapted for chemical analysis in the incompatible system, e.g., detection of organic compounds insoluble in water by aqueous ECL generation. Moreover, this microdroplet sensor has advantages of simple structure, high sensitivity, fast response and wide dynamic response, providing great promise for chemical and biological analysis.

  20. Rapid Nucleation of Iron Oxide Nanoclusters in Aqueous Solution by Plasma Electrochemistry.

    PubMed

    Bouchard, Mathieu; Létourneau, Mathieu; Sarra-Bournet, Christian; Laprise-Pelletier, Myriam; Turgeon, Stéphane; Chevallier, Pascale; Lagueux, Jean; Laroche, Gaétan; Fortin, Marc-A

    2015-07-14

    Progresses in cold atmospheric plasma technologies have made possible the synthesis of nanoparticles in aqueous solutions using plasma electrochemistry principles. In this contribution, a reactor based on microhollow cathodes and operating at atmospheric pressure was developed to synthesize iron-based nanoclusters (nanoparticles). Argon plasma discharges are generated at the tip of the microhollow cathodes, which are placed near the surface of an aqueous solution containing iron salts (FeCl2 and FeCl3) and surfactants (biocompatible dextran). Upon reaction at the plasma-liquid interface, reduction processes occur and lead to the nucleation of ultrasmall iron-based nanoclusters (IONCs). The purified IONCs were investigated by XPS and FTIR, which confirmed that the nucleated clusters contain a highly hydrated form of iron oxide, close to the stoichiometric constituents of α-FeOOH (goethite) or Fe5O3(OH)9 (ferrihydrite). Relaxivity values of r1 = 0.40 mM(-1) s(-1) and r2/r1 = 1.35 were measured (at 1.41 T); these are intermediate values between the relaxometric properties of superparamagnetic iron oxide nanoparticles used in medicine (USPIO) and those of ferritin, an endogenous contrast agent. Plasma-synthesized IONCs were injected into the mouse model and provided positive vascular signal enhancement in T1-w. MRI for a period of 10-20 min. Indications of rapid and strong elimination through the urinary and gastrointestinal tracts were also found. This study is the first to report on the development of a compact reactor suitable for the synthesis of MRI iron-based contrast media solutions, on site and upon demand.

  1. Integration of electrochemistry with ultra-performance liquid chromatography/mass spectrometry.

    PubMed

    Cai, Yi; Zheng, Qiuling; Liu, Yong; Helmy, Roy; Loo, Joseph A; Chen, Hao

    2015-01-01

    This study presents the development of ultra-performance liquid chromatography (UPLC) mass spectrometry (MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of proteins/peptides that contain disulfide bonds. In our approach, a protein/peptide mixture sample undergoes a fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and tandem mass spectrometry (MS/MS) analyses. The electrochemical cell is coupled to the mass spectrometer using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, peptides that contain disulfide bonds can be differentiated from those without disulfide bonds, as the former are electroactive and reducible. MS/MS analysis of the disulfide-reduced peptide ions provides increased information on the sequence and disulfide-linkage pattern. In a reactive DESI- MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which will be useful in top- down protein structure MS analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1(~)2 orders of magnitude by using UPLC for the liquid chromatography (LC)/EC/MS platform, in comparison to the previously used high- performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion, and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis.

  2. Etude numerique du sillage tourbillonnaire d'une eolienne

    NASA Astrophysics Data System (ADS)

    Sibuet Watters, Christophe

    Cette these formalise le concept de la surface actuatrice (SA) et en presente l'implantation dans deux methodes de mecanique des fluides assistee par ordinateur (CFD) bidimensionnelle (2D) et tridimensionnelle (3D), la validation et l'application au probleme de modelisation du sillage tourbillonnaire d'une eolienne. En termes cinetiques, une SA est une nappe tourbillonnaire qui resulte en une discontinuite de vitesse tandis qu'en termes dynamiques, elle est associee a un systeme de forces dont la composante dans la direction normale a la SA resulte en une discontinuite de pression. Les methodes CFD utilisees sont des methodes aux volumes finis, adaptees pour prendre en compte l'action de la SA sur l'ecoulement. L'approche de la SA est validee pour des problemes 2D: aile infinie et disque actuateur, ainsi que pour le probleme 3D de l'aile en translation (aile effilee), avant d'etre appliquee a plusieurs eoliennes.

  3. Conceptual difficulties experienced by senior high school students of electrochemistry: Electric circuits and oxidation-reduction equations

    NASA Astrophysics Data System (ADS)

    Garnett, Pamela J.; Treagust, David F.

    The purpose of this research was to investigate students' understanding of electrochemistry following a course of instruction. A list of conceptual and propositional knowledge statements was formulated to identify the knowledge base necessary for students to understand electric circuits and oxidation-reduction equations. The conceptual and propositional knowledge statements provided the framework for the development of a semistructured interview protocol which was administered to 32 students in their final year of high school chemistry. The interview questions about electric circuits revealed that several students in the sample were confused about the nature of electric current both in metallic conductors and in electrolytes. Students studying both physics and chemistry were more confused about current flow in metallic conductors than students who were only studying chemistry. In the section of the interview which focused on oxidation and reduction, many students experienced problems in identifying oxidation-reduction equations. Several misconceptions relating to the inappropriate use of definitions of oxidation and reduction were identified. The data illustrate how students attempted to make sense of the concepts of electrochemistry with the knowledge they had already developed or constructed. The implications of the research are that teachers, curriculum developers, and textbook writers, if they are to minimize potential misconceptions, need to be cognizant of the relationship between physics and chemistry teaching, of the need to test for erroneous preconceptions about current before teaching about electrochemical (galvanic) and electrolytic cells, and of the difficulties experienced by students when using more than one model to explain scientific phenomena.

  4. Humidity Effect on Nanoscale Electrochemistry in Solid Silver Ion Conductors and the Dual Nature of Its Locality

    DOE PAGES

    Yang, Sangmo; Strelcov, Evgheni; Paranthaman, Mariappan Parans; ...

    2015-01-07

    Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically non-local cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor.more » We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and non-local) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.« less

  5. Conceptual Difficulties Experienced by Prospective Teachers in Electrochemistry: Half-Cell Potential, Cell Potential, and Chemical and Electrochemical Equilibrium in Galvanic Cells.

    ERIC Educational Resources Information Center

    Ozkaya, Ali Riza

    2002-01-01

    A previous study of prospective teachers found that students from different countries and different levels of electrochemistry hold common misconceptions, indicating that concepts were presented to them poorly. Reports on how prospective teachers' scientifically incorrect ideas were used to form assertion-reason-type questions and how these…

  6. Magnesium-ion battery-relevant electrochemistry of MgMn2O4: crystallite size effects and the notable role of electrolyte water content

    DOE PAGES

    Yin, Jiefu; Brady, Alexander B.; Takeuchi, Esther S.; ...

    2017-03-06

    MgMn2O4 nanoparticles with crystallite sizes of 11 (MMO-1) and 31 nm (MMO-2) were synthesized and their magnesium-ion battery-relevant electrochemistry was investigated. Here, MMO-1 delivered an initial capacity of 220 mA h g–1 (678 mW h g–1). Electrolyte water content had a profound effect on cycle retention.

  7. Li/Ag2VO2PO4 batteries: the roles of composite electrode constituents on electrochemistry

    SciTech Connect

    Bock, David C.; Bruck, Andrea M.; Pelliccione, Christopher J.; Zhang, Yiman; Takeuchi, Kenneth J.; Marschilok, Amy C.; Takeuchi, Esther S.

    2016-11-01

    Silver vanadium phosphorous oxide, Ag2V2OPO4, was used as a model system to systematically study the impact on the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Three different electrode compositions were investigated.

  8. A new family of multiferrocene complexes with enhanced control of structure and stoichiometry via coordination-driven self-assembly and their electrochemistry.

    PubMed

    Yang, Hai-Bo; Ghosh, Koushik; Zhao, Yue; Northrop, Brian H; Lyndon, Matthew M; Muddiman, David C; White, Henry S; Stang, Peter J

    2008-01-23

    The design and synthesis of a new family of multiferrocene complexes with enhanced control of structure and stoichimetry via coordination-driven self-assembly is described. Insight into the structure and electronic properties of all supramolecules was obtained by electrochemical studies. The collective results provide an enhanced understanding of the influence of structural factors on the electrochemistry of multifunctional electroactive supramolecular architectures.

  9. Etude du champ magnetique dans les nuages moleculaires

    NASA Astrophysics Data System (ADS)

    Houde, Martin

    2001-12-01

    Ce travail est une étude du champ magnétique duns l'environnement circumstellaire des étoiles jeunes. Il a pour origine la certitude qu'avait l'auteur qu'il se devait d'être possible de détecter la présence d'un champ magnétique, et de possiblement le caractériser, par le biais d'observations de profils spectraux d'espèces moléculaires ioniques. Il en découle donc qu'un des buts principaux était de prouver que cela est effectivement possible. La thèse comporte alors des éléments théoriques et expérimentaux qui sont à la fois complémentaires et intimement liés. L'aspect théorique est basé sur l'interaction mutuelle que des particules neutres et chargées peuvent avoir l'une sur l'autre daps un plasma faiblement ionisé comme ceux existants daps les nuages moléculaires sites de formation stellaire. Il appert que la présence d'un champ magnétique a un effet direct sur le comportement des ions (via la force de Lorentz) et indirect sur les molécules neutres (via les nombreuses collisions entre les deux types de particules). Une telle interaction est, comme il est maintenant bien connu, présente dans les premières étapes de la formation dune étoile. Il s'agit bien sûr de la diffusion ambipolaire. Nous montrerons qu'il existe cependant un autre type de diffusion, jusqu'ici inconnue, qui se manifeste plus tard au tours de l'évolution des nuages moléculaires. Celle-ci peut avoir un effet dramatique sur l'apparence des profils spectraux (de rotation moléculaire) des espèces ioniques lorsque comparés à ceux qu'exhibent des espèces neutres coexistantes. Mais pour ce faire, il doit y avoir existence de mouvements organisés (des flots ou jets) de matière ou encore la présence de turbulence dans les régions considérées. Une distribution de vélocité du type maxwellienne ne révèlera pas la présence du champ magnétique. Les observations, qui ont pour but de confirmer la théorie, se situent dans le domaine des longueurs d

  10. Etudes physiques des mélanges eau-cryoprotecteurs

    NASA Astrophysics Data System (ADS)

    Vassoille, R.; Perez, J.

    The aim of the following review is to present the most important studies concerning the physical properties of water-solutes mixtures used in cryobiology. Cryobiology is a branch of biology which deals with the very low temperature behaviour of cells. This technique is developed today in several directions. The creation of banks of cells and perhaps in a short time of small organs, is the purpose of much research in this domain. Before freezing, living cells are generally put in a solution containing one or more solutes. The role of these solutes is to protect the cells against damage due to crystallization of water (cryoprotectors). The mechanisms of cryoprotection are not well known ; nevertheless the vitreous state formation during cooling is often invoked. So, it is possible to avoid crystallization damage such as mechanical strain (due to an increase of volume of about 10 %) and salt effects (due to osmotic pressure). The conditions in which the vitreous state is obtained, maintained during cooling, storage at low temperature and rewarming can be defined by physical studies presented in the following review. Le présent travail est essentiellement une revue bibliographique des principales études physiques qui ont été réalisées avec des solutions de composés habituellement employés en cryobiologie. La cryobiologie est une branche de la biologie qui s'intéresse au comportement des cellules à basse température. Cette discipline est actuellement en plein développement dans des domaines très divers. Son principal but est la création de banques de cellules de plus en plus complexes avec comme perspective la conservation des organes. Les cellules vivantes sont généralement placées avant congélation dans une solution contenant divers composés dont le rôle est de protéger les cellules contre les effets de la cristallisation de l'eau. L'action protectrice de ces cryoprotecteurs est encore mal connue; cependant, la formation d'un état vitreux lors du

  11. Carbon MEMS from the nanoscale to the macroscale: Novel fabrication techniques and applications in electrochemistry

    NASA Astrophysics Data System (ADS)

    Zaouk, Rabih Bachir

    Dimensional C-MEMS batteries without the need for very complex multiphysics modeling. The results show that variations in current density distributions, previously reported in the literature, were exaggerated. The work then moves to describe two other novel multiscale C-MEMS fabrication techniques that attempt to bridge the gap between macro and nano scales. The first involves the combination of electrochemistry and photolithography in order to achieve fractal like structures made entirely of carbon. The second uses a solution based deposition technique that yields fine submicron glassy carbon wires suspended between microposts hundreds of microns apart. Although previously reported in the literature, the exact fabrication mechanism of these suspended nanowires was originally attributed to the wrong mechanism. The two phase flow deposition mechanism (i.e. stretching flow) is demonstrated and the original interpretation mechanism is rebutted. It is then shown how Carbon MEMS structures can be used in a multitude of applications, e.g. dielectrophoresis, selective trapping, particle separation and manipulation.

  12. Chemistry and electrochemistry of environment-assisted cracking of an aluminum-zinc-magnesium-copper alloy

    NASA Astrophysics Data System (ADS)

    Cooper, Kevin Richard

    2001-11-01

    The mechanism of environment-assisted cracking (EAC) of 7xxx-series alloys is unclear, involving uncertain contributions of hydrogen embrittlement (HE) and anodic dissolution (AD). Fundamental understanding of the EAC mechanism is lacking in part because the role of the crack environment is not well understood. The objective of this research was to characterize and understand the role of the crack chemistry and electrochemistry during aqueous EAC of AA 7050. The crack environment can differ significantly from bulk conditions. Cations, produced by AD, hydrolyze causing local acidification; anions from the bulk electrolyte concentrate within the crack to maintain charge neutrality; ohmic potential drop results from ion migration and diffusion. A positive correlation exists between da/dt and [Al3+]Tip in chromate-chloride electrolyte wherein tip dissolution dominates flank corrosion in establishing the crack chemistry. Tip pH was 2 to 4 and determined by the reaction Al3+ + H 2O = AlOH2+ + H+. The tip potential (ETip) was approximately -0.90 VSCE and independent of EApp . The low ETip and pH promote H+ reduction, generating atomic and molecular H. Hydrogen bubbles restrict ion movement, substantially increasing the effective crack resistance over bulk conditions. Absorbed atomic hydrogen facilitates HE. The spontaneous transition from slow, incubation to high-rate da/dt coincides with the establishment of a critical aggressive tip chemistry and tip depolarization. Development of the critical occluded chemistry necessary for accelerated da/dt is a competitive process between opposing forces: AD, hydrolysis and migration promote an aggressive environment whereas diffusion reduces concentration gradients, thereby retarding the formation of an aggressive chemistry. Quantitative assessment of the contribution of tip dissolution to crack advance is hindered by a lack of knowledge of two key parameters: the tip corrosion front height and the effective crack conductivity

  13. Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

    PubMed

    Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil

    2013-05-21

    Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of

  14. Long homozygous chromosomal segments in reference families from the centre d'Etude du polymorphisme humain.

    PubMed

    Broman, K W; Weber, J L

    1999-12-01

    Using genotypes from nearly 8,000 short tandem-repeat polymorphisms typed in eight of the reference families from the Centre d'Etude du Polymorphisme Humain (CEPH), we identified numerous long chromosomal segments of marker homozygosity in many CEPH individuals. These segments are likely to represent autozygosity, the result of the mating of related individuals. Confidence that the complete segment is homozygous is gained only with markers of high density. The longest segment in the eight families spanned 77 cM and included 118 homozygous markers. All individuals in family 884 showed at least one segment of homozygosity: the father and mother were homozygous in 8 and 10 segments with an average length of 13 and 16 cM, respectively, and covering a total of 105 and 160 cM, respectively. The progeny in family 884 were homozygous over 5-16 segments with average length 11 cM. The progeny in family 102 were homozygous over 4-12 segments with average length 19 cM. Of the 100 individuals in the other six families, 1 had especially long homozygous segments, and 19 had short but significant homozygous segments. Our results indicate that long homozygous segments are common in humans and that these segments could have a substantial impact on gene mapping and health.

  15. Gastrointestinal lymphomas: the French experience of the Groupe D'etude des Lymphomes Digestifs (GELD).

    PubMed

    Ruskoné-Fourmestraux, A

    2000-01-01

    Since 1983, the French Groupe d'Etude des Lymphomes Digestifs (GELD), under the aegis of the Fondation Française de Cancérologie Digestive, has aimed to identify the different prognostic groups of the primary digestive-tract lymphomas (PDTL) and their optimal treatment. Successive multicenter studies were conducted and 91 PDTL were evaluated. A marked improvement in their prognosis was obtained by a strategy including precise histologic typing and clinical staging followed by a therapeutic approach combining initial surgical resection, whenever possible or reasonable, followed by chemotherapy adapted to the grade of malignancy and resectability of the lymphoma. The multivariate analysis indicated that the factors for good prognosis were age (< 65 yrs), gastric localisation, stage IE and radical or even incomplete surgery. However, Helicobacter pylori eradication should be the first treatment in stage IE low-grade gastric mucosa-associated lymphoid tissue (MALT) tumors. The long-term results of such medical treatment are evaluated together with the management and the place of surgery in these localised tumors. However, owing to the limited number of patients, a large international co-operative trial is needed to confirm the findings. Thirty-one cases of multiple lymphomatous polyposis were also collected and confirmed to be a distinct entity among PDTL and the gastrointestinal counterpart of the mantle-cell-zone lymphomas. High-dose radio-chemotherapy supported by auto-transplantation improved their prognosis.

  16. Etude vibroacoustique d'un systeme coque-plancher-cavite avec application a un fuselage simplifie

    NASA Astrophysics Data System (ADS)

    Missaoui, Jemai

    L'objectif de ce travail est de developper des modeles semi-analytiques pour etudier le comportement structural, acoustique et vibro-acoustique d'un systeme coque-plancher-cavite. La connection entre la coque et le plancher est assuree en utilisant le concept de rigidite artificielle. Ce concept de modelisation flexible facilite le choix des fonctions de decomposition du mouvement de chaque sous-structure. Les resultats issus de cette etude vont permettre la comprehension des phenomenes physiques de base rencontres dans une structure d'avion. Une approche integro-modale est developpee pour calculer les caracteristiques modales acoustiques. Elle utilise une discretisation de la cavite irreguliere en sous-cavites acoustiques dont les bases de developpement sont connues a priori. Cette approche, a caractere physique, presente l'avantage d'etre efficace et precise. La validite de celle-ci a ete demontree en utilisant des resultats disponibles dans la litterature. Un modele vibro-acoustique est developpe dans un but d'analyser et de comprendre les effets structuraux et acoustiques du plancher dans la configuration. La validite des resultats, en termes de resonance et de fonction de transfert, est verifiee a l'aide des mesures experimentales realisees au laboratoire.

  17. Single nanowire electrode electrochemistry of silicon anode by in situ atomic force microscopy: solid electrolyte interphase growth and mechanical properties.

    PubMed

    Liu, Xing-Rui; Deng, Xin; Liu, Ran-Ran; Yan, Hui-Juan; Guo, Yu-Guo; Wang, Dong; Wan, Li-Jun

    2014-11-26

    Silicon nanowires (SiNWs) have attracted great attention as promising anode materials for lithium ion batteries (LIBs) on account of their high capacity and improved cyclability compared with bulk silicon. The interface behavior, especially the solid electrolyte interphase (SEI), plays a significant role in the performance and stability of the electrodes. We report herein an in situ single nanowire atomic force microscopy (AFM) method to investigate the interface electrochemistry of silicon nanowire (SiNW) electrode. The morphology and Young's modulus of the individual SiNW anode surface during the SEI growth were quantitatively tracked. Three distinct stages of the SEI formation on the SiNW anode were observed. On the basis of the potential-dependent morphology and Young's modulus evolution of SEI, a mixture-packing structural model was proposed for the SEI film on SiNW anode.

  18. Using electrochemistry - total internal refection imaging ellipsometry to monitor biochemical oxygen demand on the surface tethered polyelectrolyte modified electrode

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Li, Meng; Lv, Bei'er; Chen, YanYan; Ma, Hongwei; Jin, Gang

    2015-03-01

    Our previous work has proposed an electrochemistry - total internal reflection imaging ellipsometry (EC-TIRIE) technique to observe the dissolved oxygen (DO) reduction on Clark electrode since high interface sensitivity makes TIRIE a useful tool to study redox reactions on the electrode surface. To amplify the optical signal noise ratio (OSNR), a surface tethered weak polyelectrolyte, carboxylated poly(oligo(ethylene glycol) methacrylate-random- 2-hydroxyethylmethacrylate) (abbreviated as carboxylated poly(OEGMA-r-HEMA)), has been introduced on the electrode surface. Since Clark electrode is widely used in biochemical oxygen demand (BOD) detection, we use this technique to measure BOD in the sample. The dynamic range of the system is from 0 ˜ 25 mg/L. Two samples have been measured. Compared with the conventional method, the deviation of both optical and electrical signals are less than 10%.

  19. Dual reductive/oxidative electrochemistry/liquid chromatography/mass spectrometry: Towards peptide and protein modification, separation and identification.

    PubMed

    Büter, Lars; Frensemeier, Lisa M; Vogel, Martin; Karst, Uwe

    2017-01-06

    A new hyphenated technique based on on-line dual (oxidative and reductive) electrochemistry coupled to liquid chromatography and high resolution electrospray mass spectrometry is presented. Two liquid streams are combined, with one containing a disulfide, which is reduced to the respective thiol in an electrochemical cell based on a titanium working electrode. The other stream contains phenol, which is electrochemically activated to benzoquinone on a boron-doped diamond working electrode. Upon combination of the two streams, a Michael addition takes places, leading to the covalent coupling of thiol to quinone. In continuous flow, the reaction mixture is transferred into an injection valve and the products are separated by reversed phase liquid chromatography and detected by electrospray-high resolution mass spectrometry. Proof of concept is demonstrated for low molecular mass disulfides and peptides, but further optimization will be required in future work to achieve efficient protein labelling.

  20. Further evidence for the quantum confined electrochemistry model of the formation mechanism of p - -type porous silicon

    NASA Astrophysics Data System (ADS)

    Jia, L.; Zang, S. L.; Wong, S. P.; Wilson, I. H.; Hark, S. K.; Liu, Z. F.; Cai, S. M.

    1996-11-01

    Two types of p- porous silicon (PS) were formed in HF solutions of different concentrations. One type with nanoscale (NS) dimensions of about 3 nm and the other with dimensions of about 5 nm. PS samples formed in the lower concentration of HF were anodized again in the higher concentration of HF and vice versa. The photoluminescence peak position and, thus, the size of NS units of PS were found to be related to the concentration of HF in which the PS is formed, independent of the forming time. The larger NS units of PS can be further electrochemically etched by anodization, while the smaller ones cannot. These results give a confirming evidence for the quantum confined electrochemistry model of the formation mechanism of PS based on the quantum confinement effect and classical electrochemical theory [S. L. Zhang, K. S. Ho, Y. T. Hou, B. D. Qian, P. Diao, and S. M. Cai, Appl. Phys. Lett. 62, 642 (1993)].

  1. Fast single run of vanilla fingerprint markers on microfluidic-electrochemistry chip for confirmation of common frauds.

    PubMed

    Avila, Mónica; Zougagh, Mohammed; Escarpa, Alberto; Ríos, Angel

    2009-10-01

    A new strategy based on the fast separation of the fingerprint markers of Vanilla planifolia extracts and vanilla-related samples on microfluidic-electrochemistry chip is proposed. This methodology allowed the detection of all required markers for confirmation of common frauds in this field. The elution order was strategically connected with sequential sample screening and analyte confirmation steps, where first ethyl vanillin was detected to distinguish natural from adultered samples; second, vanillin as prominent marker in V. planifolia, but frequently added in its synthetic form; and third, the final detection of the fingerprint markers (p-hydroxybenzaldehyde, vanillic acid, and p-hydroxybenzoic acid) of V. planifolia with confirmation purposes. The reliability of the proposed methodology was demonstrated in the confirmation the natural or non-natural origin of vanilla in samples using V. planifolia extracts and other selected food samples containing this flavor.

  2. Li/Ag2VO2PO4 batteries: the roles of composite electrode constituents on electrochemistry

    DOE PAGES

    Bock, David C.; Bruck, Andrea M.; Pelliccione, Christopher J.; ...

    2016-11-01

    In this study, we utilize silver vanadium phosphorous oxide, Ag2VO2PO4, as a model system to systematically study the impact of the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Notably, although highly resistive, this bimetallic cathode can be discharged as a pure electroactive material in the absence of a conductive additive as it generates an in situ conductive matrix via a reduction displacement reaction resulting in the formation of silver metal nanoparticles. Also, three different electrode compositions were investigated: Ag2VO2PO4 only, Ag2VO2PO44 with binder, and Ag2VO2PO4 with binder and carbon. Constant current discharge, pulse testing andmore » impedance spectroscopy measurements were used to characterize the electrochemical properties of the electrodes as a function of depth of discharge. In situ EDXRD was used to spatially resolve the discharge progression within the cathode by following the formation of Ag0. Ex situ XRD and EXAFS modeling were used to quantify the amount of Ag0 formed. Results indicate that the metal center reduced (V5+ or Ag+) was highly dependent on composite composition (presence of PTFE, carbon), depth of discharge (Ag0 nanoparticle formation), and spatial location within the cathode. The addition of a binder was found to increase cell polarization, and the percolation network provided by the carbon in the presence of PTFE was further increased with reduction and formation of Ag0. Lastly, this study provides insight into the factors controlling the electrochemistry of resistive active materials in composite electrodes.« less

  3. Electrochemistry of transition metal dichalcogenides: strong dependence on the metal-to-chalcogen composition and exfoliation method.

    PubMed

    Eng, Alex Yong Sheng; Ambrosi, Adriano; Sofer, Zdeněk; Šimek, Petr; Pumera, Martin

    2014-12-23

    Beyond MoS2 as the first transition metal dichalcogenide (TMD) to have gained recognition as an efficient catalyst for the hydrogen evolution reaction (HER), interest in other TMD nanomaterials is steadily beginning to proliferate. This is particularly true in the field of electrochemistry, with a myriad of emerging applications ranging from catalysis to supercapacitors and solar cells. Despite this rise, current understanding of their electrochemical characteristics is especially lacking. We therefore examine the inherent electroactivities of various chemically exfoliated TMDs (MoSe2, WS2, WSe2) and their implications for sensing and catalysis of the hydrogen evolution and oxygen reduction reactions (ORR). The TMDs studied are found to possess distinctive inherent electroactivities and together with their catalytic effects for the HER are revealed to strongly depend on the chemical exfoliation route and metal-to-chalcogen composition particularly in MoSe2. Despite its inherent activity exhibiting large variations depending on the exfoliation procedure, it is also the most efficient HER catalyst with a low overpotential of -0.36 V vs RHE (at 10 mA cm(-2) current density) and fairly low Tafel slope of ∼65 mV/dec after BuLi exfoliation. In addition, it demonstrates a fast heterogeneous electron transfer rate with a k0obs of 9.17×10(-4) cm s(-1) toward ferrocyanide, better than that seen for conventional glassy carbon electrodes. Knowledge of TMD electrochemistry is essential for the rational development of future applications; inherent TMD activity may potentially limit certain purposes, but intended objectives can nonetheless be achieved by careful selection of TMD compositions and exfoliation methods.

  4. In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

    SciTech Connect

    Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing; Laskin, Julia

    2016-11-07

    Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy. SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.

  5. Do Advance Directives Direct?

    PubMed

    Shapiro, Susan P

    2015-06-01

    Resolution of long-standing debates about the role and impact of advance directives - living wills and powers of attorney for health care - has been hampered by a dearth of appropriate data, in particular data that compare the process and outcomes of end-of-life decision making on behalf of patients with and without advance directives. Drawing on a large ethnographic study of patients in two intensive care units in a large urban teaching hospital, this article compares aspects of the medical decision-making process and outcomes by advance-directive status. Controlling for demographic characteristics and severity of illness, the study finds few significant differences between patients without advance directives and those who claim to have them. Surprisingly, these few differences hold only for those whose directives are in their hospital chart. There are no significant differences between those with no directive and those claiming to have a copy at home or elsewhere. The article considers the implications if directives seemingly must be in hand to show even modest effects. Do advance directives direct? The intensive care unit data provide far more support for the growing body of literature that casts doubt on their impact than studies that promote the use of them.

  6. Etude de la dynamique des porteurs dans des nanofils de silicium par spectroscopie terahertz

    NASA Astrophysics Data System (ADS)

    Beaudoin, Alexandre

    Ce memoire presente une etude des proprietes de conduction electrique et de la dynamique temporelle des porteurs de charges dans des nanofils de silicium sondes par rayonnement terahertz. Les cas de nanofils de silicium non intentionnellement dopes et dopes type n sont compares pour differentes configurations du montage experimental. Les mesures de spectroscopie terahertz en transmission montre qu'il est possible de detecter la presence de dopants dans les nanofils via leur absorption du rayonnement terahertz (˜ 1--12 meV). Les difficultes de modelisation de la transmission d'une impulsion electromagnetique dans un systeme de nanofils sont egalement discutees. La detection differentielle, une modification au systeme de spectroscopie terahertz, est testee et ses performances sont comparees au montage de caracterisation standard. Les instructions et des recommendations pour la mise en place de ce type de mesure sont incluses. Les resultats d'une experience de pompe optique-sonde terahertz sont egalement presentes. Dans cette experience, les porteurs de charge temporairement crees suite a l'absorption de la pompe optique (lambda ˜ 800 nm) dans les nanofils (les photoporteurs) s'ajoutent aux porteurs initialement presents et augmentent done l'absorption du rayonnement terahertz. Premierement, l'anisotropie de l'absorption terahertz et de la pompe optique par les nanofils est demontree. Deuxiemement, le temps de recombinaison des photoporteurs est etudie en fonction du nombre de photoporteurs injectes. Une hypothese expliquant les comportements observes pour les nanofils non-dopes et dopes-n est presentee. Troisiemement, la photoconductivite est extraite pour les nanofils non-dopes et dopes-n sur une plage de 0.5 a 2 THz. Un lissage sur la photoconductivite permet d'estimer le nombre de dopants dans les nanofils dopes-n. Mots-cles: nanofil, silicium, terahertz, conductivite, spectroscopie, photoconductivite.

  7. Isolation of a facultative anaerobic exoelectrogenic strain LZ-1 and probing electron transfer mechanism in situ by linking UV/Vis spectroscopy and electrochemistry.

    PubMed

    Zhou, Lei; Deng, Dandan; Zhang, Yichi; Zhou, Wen; Jiang, Yujing; Liu, Ying

    2017-04-15

    A new facultative anaerobic exoelectrogenic strain LZ-1, belonging to Citrobacter freundii, has been isolated. This strain can produce current densities of 843.9 and 865.6μAcm(-2) using citrate or acetate as carbon source in a three-electrode configuration. The electricity generation performance was also analyzed in a dual-chamber MFC system, reaching a maximum power density of 1233mWm(-2). In addition to acetate and citrate, other carbon sources such as pyruvate, formate, acetate, citrate and fumarate could also be utilized to produce current by strain LZ-1. Data supports the presence of electroactive c-type cytochromes in C. freundii sp. when grown on ITO electrodes, by linking spectroscopy and electrochemistry in situ. Since facultative strains possess many desirable properties compared to anaerobic strains, strain LZ-1 represents a promising exoelectrogenic species in engineering of biological catalysts for microbial electrochemistry. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Etude theorique et experimentale des evaporateurs de dioxyde de carbone operant dans des conditions de givrage

    NASA Astrophysics Data System (ADS)

    Bendaoud, Adlane Larbi

    Les evaporateurs de refrigeration sont surtout du type tube a ailettes, appeles serpentins, et fonctionnent dans l'une des conditions suivantes: seche, humide ou avec formation de givre. Il a ete demontre que la formation du givre sur la paroi exterieure de l'echangeur engendre une surconsommation energetique a cause des operations de degivrage puisque 15 a 20% seulement de la chaleur produite sert au degivrage tandis que le reste est dissipee dans l'environnement [1]. Avec l'avenement des nouveaux refrigerants, moins nocifs envers l'environnement, l'industrie du froid se trouve penalisee du fait que peu ou pas de composantes mecaniques (compresseur, pompe, echangeur...etc.) adaptees sont disponibles [3]. Il s'agit pour la communaute des frigoristes de combler ce retard technologique en redeveloppant ces composantes mecaniques afin qu'elles soient adaptees aux nouveaux refrigerants. Dans cette optique, et afin de mieux comprendre le comportement thermique des evaporateurs au CO2 fonctionnant dans des conditions seches, qu'un groupe de chercheurs du CanmetENERGIE avaient lance, en 2000, un programme de R & D. Dans le cadre de programme un outil de simulation des evaporateurs au CO2 a ete developpe et un banc d'essai contenant une boucle secondaire de refrigeration utilisant le CO2 comme refrigerant a ete construit. Comme continuite de ce travail de recherche, en 2006 ce meme groupe de recherche a lance un nouveau projet qui consiste a faire une etude theorique et experimentale des evaporateurs au CO2 operants dans des conditions de givrage. Et, c'est exactement dans le cadre de ce projet que se positionne ce travail de these. Ce travail de recherche a ete entrepris pour mieux comprendre le comportement thermique et hydrodynamique des serpentins fonctionnant dans des conditions de givrage, l'effet des circuits de refrigerant ainsi que celui des parametres geometriques et d'operation. Pour cela, un travail theorique supporte par une etude experimentale a ete effectue

  9. Experimental and theoretical study of possible correlation between the electrochemistry of canthin-6-one and the anti-proliferative activity against human cancer stem cells

    NASA Astrophysics Data System (ADS)

    Cebrián-Torrejón, G.; Doménech-Carbó, A.; Scotti, M. T.; Fournet, A.; Figadère, B.; Poupon, E.

    2015-12-01

    This work presents an approach to study the performance of novel targets able to overcome cancer stem cell chemoresistance, based on the voltammetric data for microparticulate films of natural or synthetic alkaloids from the canthin-6-one series. A comparison of this voltammetric technique with conventional solution phase electrochemistry suggests the differences in the anti-proliferative activity of canthin-6-ones could be tentatively correlated to their different capacity to generate semiquinone radical anions. These data also match theoretical calculations.

  10. Electrochemistry in Near-Critical and Supercritical Fluids. 4. Nitrogen Heterocycles, Nitrobenzene, and Solvated Electrons in Ammonia at Temperatures to 150C.

    DTIC Science & Technology

    1986-09-01

    of pyraz ne quinoxaline, phenazine and solvated electrons in near-critical and supercritical ammonia was investigated by cycU-i Voltanimetry and...Crooks and Allen J. Bard Department of Chemistry, University of Texas Austin, Texas 78712 ABSTRACT The electrochemistry of pyrazine, quinoxaline, phenazine ...in liquid ammonia at -40° C. The reductions of pyrazine, quinoxaline and phenazine at room temperature, and in the supercritical fluid (SCF), occur

  11. Electrochemistry and electrogenerated chemiluminescence of dithienylbenzothiadiazole derivative. Differential reactivity of donor and acceptor groups and simulations of radical cation-anion and dication-radical anion annihilations.

    PubMed

    Shen, Mei; Rodríguez-López, Joaquín; Huang, Ju; Liu, Quan; Zhu, Xu-Hui; Bard, Allen J

    2010-09-29

    We report here the electrochemistry and electrogenerated chemiluminescence (ECL) of a red-emitting dithienylbenzothiadiazole-based molecular fluorophore (4,7-bis(4-(4-sec-butoxyphenyl)-5-(3,5-di(1-naphthyl)phenyl)thiophen-2-yl)-2,1,3-benzothiadiazole, 1b). 1b contains two substituted thiophene groups as strong electron donors at the ends connected directly to a strong electron acceptor, 2,1,3-benzothiadiazole, in the center. Each thiophene moiety is substituted in position 2 by 3,5-di(1-naphthyl)phenyl and in position 3 by 4-sec-butoxyphenyl. Cyclic voltammetry of 1b, with scan rate ranging from 0.05 to 0.75 V/s, shows a single one-electron reduction wave (E°(red) = -1.18 V vs SCE) and two nernstian one-electron oxidation waves (E°(1,ox) = 1.01 V, E°(2,ox) = 1.24 V vs SCE). Reduction of the unsubstituted 2,1,3-benzothiadiazole center shows nernstian behavior with E°(red) = -1.56 V vs SCE. By comparison to a digital simulation, the heterogeneous electron-transfer rate constant for reduction, k(r)° = 1.5 × 10(-3) cm/s, is significantly smaller than those for the oxidations, k(o)° > 0.1 cm/s, possibly indicating that the two substituted end groups have a blocking effect on the reduction of the benzothiadiazole center. The ECL spectrum, produced by electron-transfer annihilation of the reduced and oxidized forms, consists of a single peak with maximum emission at about 635 nm, consistent with the fluorescence of the parent molecule. Relative ECL intensities with respect to 9,10-diphenylanthracene are 330% and 470% for the radical anion-cation and radical anion-dication annihilation, respectively. Radical anion (A(-•))-cation (A(+•)) annihilation produced by potential steps shows symmetric ECL transients during anodic and cathodic pulses, while for anion (A(-•))-dication (A(2+•)) annihilation, transient ECL shows asymmetry in which the anodic pulse is narrower than the cathodic pulse. Digital simulation of the transient ECL experiments showed that the

  12. Single-crystal-like NiO colloidal nanocrystal-aggregated microspheres with mesoporous structure: Synthesis and enhanced electrochemistry, photocatalysis and water treatment properties

    SciTech Connect

    Suo, Zhirong; Dong, Xiaonan; Liu, Hui

    2013-10-15

    A new microwave-assisted hydrothermal synthetic route based on the self-assembly and subsequently controlled thermal decomposition process is proposed to fabricate nickel oxide colloidal nanocrystal aggregated microspheres (CNAMs) with mesoporous structure. XRD, EDS, SEM, TEM. FTIR, and N{sub 2} adsorption and desorption isotherm techniques are employed for morphology and structure characterizations. The as-prepared nickel oxide CNAMs, which has a high surface area (234 m{sup 2}/g) with narrow pore distribution at around 3.25 nm, are composed of numerous hexagonal mesoporous nanocrystals of approximately 50–60 nm in size, and present a single-crystal-like characteristic. The experimental results also demonstrated that the CNAMs showed outstanding performance in electrochemistry, photocatalysis and waste water treatment due to their special hierarchical and mesoporous structure, presenting the promising candidate for catalysis and catalysis support materials. - Graphical abstract: CNAMs with mesoporous structure synthesized via a simple microwave-assisted hydrothermal method was applied in electrochemistry and catalysis and exhibited enhanced performance. Display Omitted - Highlights: • CNAMs with mesoporous structure are achieved via a simple microwave-assisted hydrothermal method. • Morphology, structure and pore distribution of sample particles is specifically controlled. • The samples show enhanced properties in electrochemistry and catalysis due to hierarchical structure.

  13. 99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

    PubMed

    McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

    2012-08-20

    The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

  14. Etude de la Region de Transition A=130: Structure a Spin Eleve des Noyaux de SAMARIUM-136 et SAMARIUM-138

    NASA Astrophysics Data System (ADS)

    Nadon, Normand

    La structure a haut spin des noyaux pairs-pairs de ^{136}Sm et ^{138}Sm a ete etudiee a l'aide du spectrometre 8pi de Chalk River. Les noyaux etaient produits par une reaction d'ions lourds. La mesure des cascades gamma emises lors de la desexcitation du noyau nous a permis d'etablir le schema de niveaux des noyaux de ^{136 }Sm et ^{138}Sm jusqu'a un spin de 30hbar. Nous avons mis en evidence plusieurs nouvelles bandes rotationnelles. A partir des calculs theoriques CSM (Cranked Shell Model), nous avons identifie les differentes configurations responsables de l'excitation de ces noyaux. Dans ces deux noyaux, on assiste a une competition entre les neutrons provenant du haut de la couche h_{11/2 } et les protons issus du bas de la meme couche. D'autres calculs TRS (Total Routhian Surface) nous ont permis de suivre l'evolution du noyau en fonction de la deformation. Les resultats montrent que ces noyaux se situent dans une region de transition entre une forme allongee et une forme aplatie. D'apres notre etude, meme si les neutrons entrai nent le noyau vers une forme aplatie, la presence des protons stabilise le noyau a une forme triaxiale. De l'experience effectuee sur le noyau de ^{136}Sm, nous avons observe quelques evidences d'une bande superdeformee. Cette bande serait batie sur une configuration a plusieurs quasiparticules impliquant possiblement l'orbitale nu i_ {13/2}. La decouverte de cette bande superdeformee vient corroborer les predictions theoriques. Cependant, une etude plus approfondie devra etre entreprise afin de valider la structure de cette bande.

  15. Etude de la performance des radars hautes-frequences CODAR et WERA pour la mesure des courants marins en presence partielle de glace de mer

    NASA Astrophysics Data System (ADS)

    Kamli, Emna

    Les radars hautes-frequences (RHF) mesurent les courants marins de surface avec une portee pouvant atteindre 200 kilometres et une resolution de l'ordre du kilometre. Cette etude a pour but de caracteriser la performance des RHF, en terme de couverture spatiale, pour la mesure des courants de surface en presence partielle de glace de mer. Pour ce faire, les mesures des courants de deux radars de type CODAR sur la rive sud de l'estuaire maritime du Saint-Laurent, et d'un radar de type WERA sur la rive nord, prises pendant l'hiver 2013, ont ete utilisees. Dans un premier temps, l'aire moyenne journaliere de la zone ou les courants sont mesures par chaque radar a ete comparee a l'energie des vagues de Bragg calculee a partir des donnees brutes d'acceleration fournies par une bouee mouillee dans la zone couverte par les radars. La couverture des CODARs est dependante de la densite d'energie de Bragg, alors que la couverture du WERA y est pratiquement insensible. Un modele de fetch appele GENER a ete force par la vitesse du vent predite par le modele GEM d'Environnement Canada pour estimer la hauteur significative ainsi que la periode modale des vagues. A partir de ces parametres, la densite d'energie des vagues de Bragg a ete evaluee pendant l'hiver a l'aide du spectre theorique de Bretschneider. Ces resultats permettent d'etablir la couverture normale de chaque radar en absence de glace de mer. La concentration de glace de mer, predite par le systeme canadien operationnel de prevision glace-ocean, a ete moyennee sur les differents fetchs du vent selon la direction moyenne journaliere des vagues predites par GENER. Dans un deuxieme temps, la relation entre le ratio des couvertures journalieres obtenues pendant l'hiver 2013 et des couvertures normales de chaque radar d'une part, et la concentration moyenne journaliere de glace de mer d'autre part, a ete etablie. Le ratio des couvertures decroit avec l'augmentation de la concentration de glace de mer pour les deux types

  16. Conducting Polymer Nanostructures and Nanocomposites with Carbon Nanotubes: Hierarchical Assembly by Molecular Electrochemistry, Growth Aspects and Property Characterization.

    PubMed

    Gupta, Sanju; Price, Carson; Heintzman, Eli

    2016-01-01

    Conducting (or π-conjugated) polymers are promising materials for preparing supramolecular nano-structures and nanocomposites. We report controlled nanostructure syntheses of polypyrrole (PPy) and poylaniline (PANi) via electropolymerization (i.e., in-situ electrochemical anodic oxidation). The density, shape, caliber and thickness of self-assembled PPy micro-containers are regulated by electrochemical potential window for H2 bubbles and number of cyclic voltammetric (potentiodynamic) scans. Likewise, we employed amperometry, chronopotentiometry and potentiodynamic modes using hydrochloric acid as oxidizing agent to prepare PANi nanoparticles and nanotubules. We present our findings from the viewpoint of molecular electrochemistry with growth kinetic aspects yielding mechanistic details (initially forming dimers and oligomers as nucleating agents followed by polymer growth). Also targeted is forming nanocomposites with functionalized single- and multi-walled carbon nanotubes (FSWCNTs and FMWCNTs) as reinforced agent to optimize structural and functional properties. All of these novel nanomaterials are characterized using a range of complementary techniques to establish microscopic structure-property-function relationship.

  17. Surface analysis and electrochemistry of a robust carbon-nanofiber-based electrode platform H2O2 sensor

    NASA Astrophysics Data System (ADS)

    Suazo-Dávila, D.; Rivera-Meléndez, J.; Koehne, J.; Meyyappan, M.; Cabrera, C. R.

    2016-10-01

    A vertically aligned carbon nanofiber-based (VACNF) electrode platform was developed for an enzymeless hydrogen peroxide sensor. Vertical nanofibers have heights on the order of 2-3 μm, and diameters that vary from 50 to 100 nm as seen by atomic force microscopy. The VACNF was grown as individual, vertically, and freestanding structures using plasma-enhanced chemical vapor deposition. The electrochemical sensor, for the hydrogen peroxide measurement in solution, showed stability and reproducibility in five consecutive calibration curves with different hydrogen peroxide concentrations over a period of 3 days. The detection limit was 66 μM. The sensitivity for hydrogen peroxide electrochemical detection was 0.0906 mA cm-2 mM-1, respectively. The sensor was also used for the measurement of hydrogen peroxide as the by-product of the reaction of cholesterol with cholesterol oxidase as a biosensor application. The sensor exhibits linear behavior in the range of 50 μM-1 mM in cholesterol concentrations. The surface analysis and electrochemistry characterization is presented.

  18. Impact of Soil Composition and Electrochemistry on Corrosion of Rock-cut Slope Nets along Railway Lines in China

    PubMed Central

    Chen, Jiao; Chen, Zhaoqiong; Ai, Yingwei; Xiao, Jingyao; Pan, Dandan; Li, Wei; Huang, Zhiyu; Wang, Yumei

    2015-01-01

    Taking the slope of Suiyu Railway to study, the research separately studied soil resistivity, soil electrochemistry (corrosion potential, oxidization reduction potential, electric potential gradient and pH), soil anions (total soluble salt, Cl−, SO42− and ), and soil nutrition (moisture content, organic matter, total nitrogen, alkali-hydrolysable nitrogen, available phosphorus, and available potassium) at different slope levels, and conducted corrosion grade evaluation on artificial soil according to its single index and comprehensive indexes. Compared with other factors, water has the biggest impact on the corrosion of slope protection net, followed by anion content. Total soluble salt has the moderate impact on the corrosion of slope protection net, and stray current has the moderate impact on the corrosion of mid-slope protection net. Comprehensive evaluation on the corrosive degree of soil samples indicates that the corrosion of upper slope is moderate, and the corrosion of mid-slope and lower slope is strong. Organic matter in soil is remarkably relevant to electric potential gradient. Available nitrogen, available potassium and available phosphorus are remarkably relevant to anions. The distribution of soil nutrient is indirectly relevant to slope type. PMID:26450811

  19. Electrochemistry at nanoscale electrodes: individual single-walled carbon nanotubes (SWNTs) and SWNT-templated metal nanowires.

    PubMed

    Dudin, Petr V; Snowden, Michael E; Macpherson, Julie V; Unwin, Patrick R

    2011-12-27

    Individual nanowires (NWs) and native single-walled carbon nanotubes (SWNTs) can be readily used as well-defined nanoscale electrodes (NSEs) for voltammetric analysis. Here, the simple photolithography-free fabrication of submillimeter long Au, Pt, and Pd NWs, with sub-100 nm heights, by templated electrodeposition onto ultralong flow-aligned SWNTs is demonstrated. Both individual Au NWs and SWNTs are employed as NSEs for electron-transfer (ET) kinetic quantification, using cyclic voltammetry (CV), in conjunction with a microcapillary-based electrochemical method. A small capillary with internal diameter in the range 30-70 μm, filled with solution containing a redox-active mediator (FcTMA(+) ((trimethylammonium)methylferrocene), Fe(CN)(6)(4-), or hydrazine) is positioned above the NSE, so that the solution meniscus completes an electrochemical cell. A 3D finite-element model, faithfully reproducing the experimental geometry, is used to both analyze the experimental CVs and derive the rate of heterogeneous ET, using Butler-Volmer kinetics. For a 70 nm height Au NW, intrinsic rate constants, k(0), up to ca. 1 cm s(-1) can be resolved. Using the same experimental configuration the electrochemistry of individual SWNTs can also be accessed. For FcTMA(+/2+) electrolysis the simulated ET kinetic parameters yield very fast ET kinetics (k(0) > 2 ± 1 cm s(-1)). Some deviation between the experimental voltammetry and the idealized model is noted, suggesting that double-layer effects may influence ET at the nanoscale.

  20. Dispersion of Nanocrystalline Fe 3 O 4 within Composite Electrodes: Insights on Battery-Related Electrochemistry

    SciTech Connect

    Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei; Wang, Jiajun; Knehr, K. W.; Wang, Jun; Wang, Feng; West, Alan C.; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.

    2016-04-20

    Aggregation of nanosized materials in composite lithium-ion-battery electrodes can be a significant factor influencing electrochemical behavior. In this study, aggregation was controlled in magnetite, Fe3O4, composite electrodes via oleic acid capping and subsequent dispersion in a carbon black matrix. A heat treatment process was effective in the removal of the oleic acid capping agent while preserving a high degree of Fe3O4 dispersion. Electrochemical testing showed that Fe3O4 dispersion is initially beneficial in delivering a higher functional capacity, in agreement with continuum model simulations. However, increased capacity fade upon extended cycling was observed for the dispersed Fe3O4 composites relative to the aggregated Fe3O4 composites. X-ray absorption spectroscopy measurements of electrodes post cycling indicated that the dispersed Fe3O4 electrodes are more oxidized in the discharged state, consistent with reduced reversibility compared with the aggregated sample. Higher charge-transfer resistance for the dispersed sample after cycling suggests increased surface-film formation on the dispersed, high-surface-area nanocrystalline Fe3O4 compared to the aggregated materials. This study provides insight into the specific effects of aggregation on electrochemistry through a multiscale view of mechanisms for magnetite composite electrodes.

  1. Impact of Soil Composition and Electrochemistry on Corrosion of Rock-cut Slope Nets along Railway Lines in China.

    PubMed

    Chen, Jiao; Chen, Zhaoqiong; Ai, Yingwei; Xiao, Jingyao; Pan, Dandan; Li, Wei; Huang, Zhiyu; Wang, Yumei

    2015-10-09

    Taking the slope of Suiyu Railway to study, the research separately studied soil resistivity, soil electrochemistry (corrosion potential, oxidization reduction potential, electric potential gradient and pH), soil anions (total soluble salt, Cl(-), SO4(2-) and ), and soil nutrition (moisture content, organic matter, total nitrogen, alkali-hydrolysable nitrogen, available phosphorus, and available potassium) at different slope levels, and conducted corrosion grade evaluation on artificial soil according to its single index and comprehensive indexes. Compared with other factors, water has the biggest impact on the corrosion of slope protection net, followed by anion content. Total soluble salt has the moderate impact on the corrosion of slope protection net, and stray current has the moderate impact on the corrosion of mid-slope protection net. Comprehensive evaluation on the corrosive degree of soil samples indicates that the corrosion of upper slope is moderate, and the corrosion of mid-slope and lower slope is strong. Organic matter in soil is remarkably relevant to electric potential gradient. Available nitrogen, available potassium and available phosphorus are remarkably relevant to anions. The distribution of soil nutrient is indirectly relevant to slope type.

  2. Silver Vanadium Diphosphate Ag2VP2O8: Electrochemistry and Characterization of Reduced Material providing Mechanistic Insights

    PubMed Central

    Takeuchi, Esther S.; Lee, Chia-Ying; Chen, Po-Jen; Menard, Melissa C.; Marschilok, Amy C.; Takeuchi, Kenneth J.

    2013-01-01

    Silver vanadium phosphorous oxides (AgwVxPyOz) are notable battery cathode materials due to their high energy density and demonstrated ability to form in-situ Ag metal nanostructured electrically conductive networks within the cathode. While analogous silver vanadium diphosphate materials have been prepared, electrochemical evaluations of these diphosphate based materials have been limited. We report here the first electrochemical study of a silver vanadium diphosphate, Ag2VP2O8, where the structural differences associated with phosphorous oxides versus diphosphates profoundly affect the associated electrochemistry. Reminiscent of Ag2VO2PO4 reduction, in-situ formation of silver metal nanoparticles was observed with reduction of Ag2VP2O8. However, counter to Ag2VO2PO4 reduction, Ag2VP2O8 demonstrates a significant decrease in conductivity upon continued electrochemical reduction. Structural analysis contrasting the crystallography of the parent Ag2VP2O8 with that of the proposed Li2VP2O8 reduction product is employed to gain insight into the observed electrochemical reduction behavior, where the structural rigidity associated with the diphosphate anion may be associated with the observed particle fracturing upon deep electrochemical reduction. Further, the diphosphate anion structure may be associated with the high thermal stability of the partially reduced Ag2VP2O8 materials, which bodes well for enhanced safety of batteries incorporating this material. PMID:25866419

  3. A battery model that fully couples mechanics and electrochemistry at both particle and electrode levels by incorporation of particle interaction

    NASA Astrophysics Data System (ADS)

    Wu, Bin; Lu, Wei

    2017-08-01

    This paper develops a multi-scale mechanical-electrochemical model which enables fully coupled mechanics and electrochemistry at both particle and electrode levels. At the particle level, solid diffusion is modeled using a generalized chemical potential to capture the effects of mechanical stress and phase transformation. At the electrode level, the stress arising from particle interaction is incorporated in a continuum model. This particle interaction stress is in addition to the traditional concept of intercalation stress inside isolated particles. The particle and continuum electrode levels are linked by the particle interaction stress as loads on the particle surface, and by consideration of stress on the electrochemical reaction rate on the particle surface. The effect of mechanical stress on electrochemical reaction results in a stress-dependent over-potential between particle and electrolyte. Stress gradient in an electrode leads to inhomogeneous intercalation/deintercalation currents for particles depending on their interaction stress with neighbors, resulting in stress gradient induced inhomogeneous state of charge. Conversely, non-uniform intercalation/deintercalation currents in an electrode lead to stress between particles. With this model we have an important finding: an electrochemically inactive region in an electrode causes stress built-up. This model provides a powerful tool to address various problems such as fracture in-between particles.

  4. Impact of Soil Composition and Electrochemistry on Corrosion of Rock-cut Slope Nets along Railway Lines in China

    NASA Astrophysics Data System (ADS)

    Chen, Jiao; Chen, Zhaoqiong; Ai, Yingwei; Xiao, Jingyao; Pan, Dandan; Li, Wei; Huang, Zhiyu; Wang, Yumei

    2015-10-01

    Taking the slope of Suiyu Railway to study, the research separately studied soil resistivity, soil electrochemistry (corrosion potential, oxidization reduction potential, electric potential gradient and pH), soil anions (total soluble salt, Cl-, SO42- and ), and soil nutrition (moisture content, organic matter, total nitrogen, alkali-hydrolysable nitrogen, available phosphorus, and available potassium) at different slope levels, and conducted corrosion grade evaluation on artificial soil according to its single index and comprehensive indexes. Compared with other factors, water has the biggest impact on the corrosion of slope protection net, followed by anion content. Total soluble salt has the moderate impact on the corrosion of slope protection net, and stray current has the moderate impact on the corrosion of mid-slope protection net. Comprehensive evaluation on the corrosive degree of soil samples indicates that the corrosion of upper slope is moderate, and the corrosion of mid-slope and lower slope is strong. Organic matter in soil is remarkably relevant to electric potential gradient. Available nitrogen, available potassium and available phosphorus are remarkably relevant to anions. The distribution of soil nutrient is indirectly relevant to slope type.

  5. Effect of alpha-cyclodextrin on drug distribution studied by electrochemistry at interfaces between immiscible electrolyte solutions.

    PubMed

    Deryabina, Maria A; Hansen, Steen H; Østergaard, Jesper; Jensen, Henrik

    2009-05-21

    The description and understanding of noncovalent interactions and distribution of potential new drug compounds in an organism is of paramount importance for the successful development of new drugs. In this work, a new procedure based on electrochemistry at the interface between two immiscible electrolyte solutions (ITIES) for addressing and discriminating between drug compound/ligand interactions in aqueous solution and nonspecific ligand effects on oil-water distribution behavior has been developed. The procedure is demonstrated using five drug compounds with different physical chemical parameters and alpha-cyclodextrin as the aqueous phase ligand. Alpha-cyclodextrin was chosen as an aqueous phase ligand, as it is frequently used in drug formulations to enhance solubility and bioavailability of drug compounds. Supplementary capillary electrophoresis experiments provided more detailed information on alpha-cyclodextrin drug complexation and, in combination with the electrochemical studies, provided information on solvation effects affecting the oil-water distribution of the drug compounds. The use of ligand shift ion partition diagrams for data presentation is a convenient format for the visualization of ligand effects on distribution behavior of related drug compounds.

  6. Etude Exploratoire sur l’Etat de Stress Post-Traumatique dans Deux Unites Operationnelles de l’Armee de Terre (Exploratory Study of the Condition of Post-Traumatic Stress Disorder from Two Operational Units of Ground Forces)

    DTIC Science & Technology

    2006-04-01

    RTO-MP-HFM-134 30 - 1 Etude exploratoire sur l’état de stress post-traumatique dans deux unités opérationnelles de l’armée de terre D ...Leur diagnostic nécessite une démarche active du médecin. L’objectif de l’étude vise à évaluer la fréquence de cette pathologie dans une population...d’inhibition (1). Cette pathologie a fréquemment une évolution chronique. Elle peut être très invalidante. Vallet, D .; Arvers, P. (2006) Etude exploratoire

  7. Insight in layer-by-layer assembly of cysteamine and L-cysteine on the copper surface by electrochemistry and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Song, Ping; Shen, Shu; Li, Chuan-Chuan; Guo, Xiao-Yu; Wen, Ying; Yang, Hai-Feng

    2015-02-01

    In this work, we examined the relationship between the anticorrosion behavior and the structure of the cysteamine/L-cysteine layer-by-layer coating on the copper surface via the self-assembled monolayers (SAMs) technique with electrochemistry and surface-enhanced Raman scattering (SERS) spectroscopy. SERS results elucidated the layer-by-layer adsorption mechanism of cysteamine/L-cysteine at the copper surface. Electrochemical investigations explored the inhibition behavior of cysteamine/L-cysteine for copper from corrosion with a high protection efficiency of 91.4%.

  8. Modeling of Pressurized Electrochemistry and Steam-Methane Reforming in Solid Oxide Fuel Cells and the Effects on Thermal and Electrical Stack Performance

    SciTech Connect

    Recknagle, Kurtis P.; Khaleel, Mohammad A.

    2009-03-01

    Summarizes work done to extend the electrochemical performance and methane reforming submodels to include the effects of pressurization and to demonstrate this new modeling capability by simulating large stacks operating on methane-rich fuel under pressurized and non-pressurized conditions. Pressurized operation boosts electrochemical performance, alters the kinetics of methane reforming, and effects the equilibrium composition of methane fuels. This work developed constitutive submodels that couple the electrochemistry, reforming, and pressurization to yield an increased capability of the modeling tool for prediction of SOFC stack performance.

  9. Synthesis, photophysics, electrochemistry, thermal stability and electroluminescent performances of a new europium complex with bis(β-diketone) ligand containing carbazole group.

    PubMed

    Liu, Jian; Liang, Quan-Bin; Wu, Hong-Bin

    2016-09-07

    We synthesized a new europium complex [Eu(ecbpd)3 (Phen)] with bis(β-diketone) ligand containing a carbazole group, in which ecbpd and Phen are dehydro-3,3'-(9-ethyl-9H-carbazole-3,6-diyl)bis(1-phenylpropane-1,3-dione) and 1,10-phenanthroline, respectively. Its UV/vis and photoluminescent spectra, quantum yield, luminescence lifetime, electrochemistry, thermal stability and electroluminescent performances were studied. This europium complex showed low efficiency luminescence, which is probably due to the mismatching energy levels of its ligand and Eu(3)(+) , as well as the double Eu(3)(+) core resonance.

  10. La structure de l'eau liquide: Une etude thermique par spectroscopie infrarouge

    NASA Astrophysics Data System (ADS)

    Larouche, Pascal

    Le probleme de la structure de l'eau liquide est important car l'eau est le liquide le plus present sur Terre, et complexe, la quete d'un modele precis pour decrire comment fonctionne ce liquide ayant debute des la fin du dix-neuvieme siecle. Cette etude aborde ce probleme en etudiant l'effet de l'augmentation de la temperature sur H2O et D 2O purs a l'aide de la spectroscopie infrarouge. L'intervalle de temperatures scrute est 29--93.1°C. Les spectres enregistres sont des spectres MIR-ATR entre 650 et 6000 cm-1 . L'analyse par facteurs de ces donnees permet de montrer que deux et seulement deux facteurs principaux sont necessaires pour decomposer tous les spectres experimentaux. Ces resultats sont confirmes grace a l'analyse par facteurs de spectres de la region FIR. Par la suite, la transformation en spectres de la partie reelle n et imaginaire k de l'indice de refraction permet de combiner les donnees des regions MIR et FIR. Une fois ce calcul termine, les spectres de transmission complets de H 2O et D2O entre 25 et 90°C sont connus. Ils sont ensuite utilises pour calculer par extrapolation le spectre des especes constituant l'eau liquide, puis leur abondance en fonction de la temperature. L'extrapolation de ces abondances montre que les especes correspondent a des temperatures limites de --18 et 122°C. Par la suite, la decomposition gaussienne des spectres d'especes met en evidence la riche structure de ces objets et permet de demontrer que l'apparent deplacement du massif d'absorption OH (OD) est produit par une variation de l'intensite des bandes et non pas de leur deplacement. L'examen attentif des spectres des especes prouve qu'il n'y a pas de OH libres crees par l'augmentation de la temperature: meme a 93.1°C, chaque molecule possede quatre liens-H. Ces conclusions sont de plus confirmees par une analyse thermodynamique du passage des molecules de la phase solide a la phase gazeuse. Pour diversifier la nature des resultats experimentaux utilises, des

  11. Etude par spectroscopie de Coulomb de points quantiques lateraux individuels et couples

    NASA Astrophysics Data System (ADS)

    Pioro-Ladriere, Michel

    Des points quantiques contenant un nombre discret et variable d'electrons sont formes dans un gaz bi-dimensionnel d'electrons a l'aide de grilles metalliques. Le transport electrique, le blocage de spin et la detection de charge sont employes comme outils spectroscopiques permettant de sonder les proprietes de ces nanostructures. Ces techniques permettent aussi de controler exactement le nombres d'electrons confines dans des points quantiques individuels et couples en utilisant un patron de grille judicieux. Une technique de refroidissement en tension est developpee afin de minimiser les effets parasites du bruit telegraphique. Ce type de bruit de charge deteriore la stabilite des nanostructures laterales par l'activation d'un minuscule courant de fuite entre les grilles et le gaz bi-dimensionnel. Un modele expliquant le role du refroidissement en tension sur le courant de fuite est presente. L'activation du courant de fuite est confirmee par detection de charge. Les effets des interactions entre les electrons pieges dans un point quantique sont ensuite etudies dans un regime ou il est possible de comparer les resulats experimentaux avec ceux obtenus par diagonalisation exacte. L'etude demontre que la phase associee au facteur de remplissage nu = 2 est instable au-dessus d'un nombre critique d'electrons. Cette instabilite est confirmee experimentalement par blocage de spin. On demontre aussi l'existence d'etats correles dans le regime des renversements de spin, associe au passage de la phase nu = 2 a nu = 1. Les etats correles sont identifies par spectroscopie en transport non lineaire. Cette caracterisation du diagramme de phase de points individuels permet de coupler deux points quantiques configures a nu = 2. Pour ce regime, la nanostructure se comporte comme un systeme a deux niveaux pouvant contenir entre un et quatre electrons de valence et ce, meme si le nombre total d'electrons est plus eleve. Les degres de liberte de charge et de spin des deux points

  12. Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 (M = Mn, Fe).

    PubMed

    Laha, S; Natarajan, S; Gopalakrishnan, J; Morán, E; Sáez-Puche, R; Alario-Franco, M Á; Dos Santos-Garcia, A J; Pérez-Flores, J C; Kuhn, A; García-Alvarado, F

    2015-02-07

    We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to

  13. Fully solar-driven thermo- and electrochemistry for advanced oxidation processes (STEP-AOPs) of 2-nitrophenol wastewater.

    PubMed

    Nie, Chunhong; Shao, Nan; Wang, Baohui; Yuan, Dandan; Sui, Xin; Wu, Hongjun

    2016-07-01

    The STEP (Solar Thermal Electrochemical Process) for Advanced Oxidation Processes (AOPs, combined to STEP-AOPs), fully driven by solar energy without the input of any other forms of energy and chemicals, is introduced and demonstrated from the theory to experiments. Exemplified by the persistent organic pollutant 2-nitrophenol in water, the fundamental model and practical system are exhibited for the STEP-AOPs to efficiently transform 2-nitrophenol into carbon dioxide, water, and the other substances. The results show that the STEP-AOPs system performs more effectively than classical AOPs in terms of the thermodynamics and kinetics of pollutant oxidation. Due to the combination of solar thermochemical reactions with electrochemistry, the STEP-AOPs system allows the requisite electrolysis voltage of 2-nitrophenol to be experimentally decreased from 1.00 V to 0.84 V, and the response current increases from 18 mA to 40 mA. STEP-AOPs also greatly improve the kinetics of the oxidation at 30 °C and 80 °C. As a result, the removal rate of 2-nitrophenol after 1 h increased from 19.50% at 30 °C to 32.70% at 80 °C at constant 1.90 V. Mechanistic analysis reveals that the oxidation pathway is favorably changed because of thermal effects. The tracking of the reaction displayed that benzenediol and hydroquinone are initial products, with maleic acid and formic acid as sequential carboxylic acid products, and carbon dioxide as the final product. The theory and experiments on STEP-AOPs system exemplified by the oxidation of 2-nitrophenol provide a broad basis for extension of the STEP and AOPs for rapid and efficient treatment of organic wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

    PubMed Central

    Johnson, Grant E.; Wang, Bingbing; Laskin, Julia

    2016-01-01

    Molecular-level understanding of electrochemical processes occurring at electrode–electrolyte interfaces (EEIs) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and application of solid-state in situ thin-film electrochemical cells to explore redox and catalytic processes occurring at well-defined EEIs generated using soft-landing (SL) of mass- and charge-selected cluster ions. In situ cells with excellent mass-transfer properties are fabricated using carefully designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy. SL is, therefore, demonstrated to be a unique tool for studying fundamental processes occurring at EEIs. Using an aprotic cell, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEIs with POM anions generated by electrospray ionization and gas-phase dissociation. Additionally, a proton-conducting cell has been developed to characterize the oxygen reduction activity of bare Pt clusters (Pt30 ∼1 nm diameter), thus demonstrating the capability of the cell for probing catalytic reactions in controlled gaseous environments. By combining the developed in situ electrochemical cell with ion SL we established a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely defined conditions. This capability will advance the molecular-level understanding of processes occurring at EEIs that are critical to many energy-related technologies. PMID:27821731

  15. In situ solid-state electrochemistry of mass-selected ions at well-defined electrode-electrolyte interfaces.

    PubMed

    Prabhakaran, Venkateshkumar; Johnson, Grant E; Wang, Bingbing; Laskin, Julia

    2016-11-22

    Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEIs) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and application of solid-state in situ thin-film electrochemical cells to explore redox and catalytic processes occurring at well-defined EEIs generated using soft-landing (SL) of mass- and charge-selected cluster ions. In situ cells with excellent mass-transfer properties are fabricated using carefully designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy. SL is, therefore, demonstrated to be a unique tool for studying fundamental processes occurring at EEIs. Using an aprotic cell, the effect of charge state ([Formula: see text]) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEIs with POM anions generated by electrospray ionization and gas-phase dissociation. Additionally, a proton-conducting cell has been developed to characterize the oxygen reduction activity of bare Pt clusters (Pt30 ∼1 nm diameter), thus demonstrating the capability of the cell for probing catalytic reactions in controlled gaseous environments. By combining the developed in situ electrochemical cell with ion SL we established a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely defined conditions. This capability will advance the molecular-level understanding of processes occurring at EEIs that are critical to many energy-related technologies.

  16. Probing Protein 3D Structures and Conformational Changes Using Electrochemistry-Assisted Isotope Labeling Cross-Linking Mass Spectrometry.

    PubMed

    Zheng, Qiuling; Zhang, Hao; Wu, Shiyong; Chen, Hao

    2016-05-01

    This study presents a new chemical cross-linking mass spectrometry (MS) method in combination with electrochemistry and isotope labeling strategy for probing both protein three-dimensional (3D) structures and conformational changes. For the former purpose, the target protein/protein complex is cross-linked with equal mole of premixed light and heavy isotope labeled cross-linkers carrying electrochemically reducible disulfide bonds (i.e., DSP-d0 and DSP-d8 in this study, DSP = dithiobis[succinimidyl propionate]), digested and then electrochemically reduced followed with online MS analysis. Cross-links can be quickly identified because of their reduced intensities upon electrolysis and the presence of doublet isotopic peak characteristics. In addition, electroreduction converts cross-links into linear peptides, facilitating MS/MS analysis to gain increased information about their sequences and modification sites. For the latter purpose of probing protein conformational changes, an altered procedure is adopted, in which the protein in two different conformations is cross-linked using DSP-d0 and DSP-d8 separately, and then the two protein samples are mixed in 1:1 molar ratio. The merged sample is subjected to digestion and electrochemical mass spectrometric analysis. In such a comparative cross-linking experiment, cross-links could still be rapidly recognized based on their responses to electrolysis. More importantly, the ion intensity ratios of light and heavy isotope labeled cross-links reveal the conformational changes of the protein, as exemplified by examining the effect of Ca(2+) on calmodulin conformation alternation. This new cross-linking MS method is fast and would have high value in structural biology. Graphical Abstract ᅟ.

  17. A multi-site array for combined local electrochemistry and electrophysiology in the non-human primate brain.

    PubMed

    Disney, Anita A; McKinney, Collin; Grissom, Larry; Lu, Xuekun; Reynolds, John H

    2015-11-30

    Currently, the primary technique employed in circuit-level study of the brain is electrophysiology, recording local field or action potentials (LFPs or APs). However most communication between neurons is chemical and the relationship between electrical activity within neurons and chemical signaling between them is not well understood in vivo, particularly for molecules that signal at least in part by non-synaptic transmission. We describe a multi-contact array and accompanying head stage circuit that together enable concurrent electrophysiological and electrochemical recording. The array is small (<200 μm) and can be assembled into a device of arbitrary length. It is therefore well-suited for use in all major in vivo model systems in neuroscience, including non-human primates where the large brain and need for daily insertion and removal of recording devices places particularly strict demands on design. We present a protocol for array fabrication. We then show that a device built in the manner described can record LFPs and perform enzyme-based amperometric detection of choline in the awake macaque monkey. Comparison with existing methods Existing methods allow single mode (electrophysiology or electrochemistry) recording. This system is designed for concurrent, dual-mode recording. It is also the only system designed explicitly to meet the challenges of recording in non-human primates. Our system offers the possibility for conducting in vivo studies in a range of species that examine the relationship between the electrical activity of neurons and their chemical environment, with exquisite spatial and temporal precision. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  18. A multi-site array for combined local electrochemistry and electrophysiology in the non-human primate brain

    PubMed Central

    Disney, Anita A; McKinney, Collin; Grissom, Larry; Lu, Xuekun; Reynolds, John H

    2015-01-01

    Background Currently, the primary technique employed in circuit-level study of the brain is electrophysiology, recording local field or action potentials (LFPs or APs). However most communication between neurons is chemical and the relationship between electrical activity within neurons and chemical signaling between them is not well understood in vivo, particularly for molecules that signal at least in part by non-synaptic transmission. New Method We describe a multi-contact array and accompanying head stage circuit that together enable concurrent electrophysiological and electrochemical recording. The array is small (<200μm) and can be assembled into a device of arbitrary length. It is therefore well-suited for use in all major in vivo model systems in neuroscience, including non-human primates where the large brain and need for daily insertion and removal of recording devices places particularly strict demands on design. Results We present a protocol for array fabrication. We then show that a device built in the manner described can record LFPs and perform enzyme-based amperometric detection of choline in the awake macaque monkey. Comparison with existing methods Existing methods allow single mode (electrophysiology or electrochemistry) recording. This system is designed for concurrent, dual-mode recording. It is also the only system designed explicitly to meet the challenges of recording in non-human primates. Conclusions Our system offers the possibility for conducting in vivo studies in a range of species that examine the relationship between the electrical activity of neurons and their chemical environment, with exquisite spatial and temporal precision. PMID:26226654

  19. A quantitative assay for reductive metabolism of a pesticide in fish using electrochemistry coupled with liquid chromatography tandem mass spectrometry.

    PubMed

    Bussy, Ugo; Chung-Davidson, Yu-Wen; Li, Ke; Li, Weiming

    2015-04-07

    This is the first study to use electrochemistry to generate a nitro reduction metabolite as a standard for a liquid chromatography-mass spectrometry-based quantitative assay. This approach is further used to quantify 3-trifluoromethyl-4-nitrophenol (TFM) reductive metabolism. TFM is a widely used pesticide for the population control of sea lamprey (Petromyzon marinus), an invasive species of the Laurentian Great Lakes. Three animal models, sea lamprey, lake sturgeon (Acipenser fulvescens), and rainbow trout (Oncorhynchus mykiss), were selected to evaluate TFM reductive metabolism because they have been known to show differential susceptibilities to TFM toxicity. Amino-TFM (aTFM; 3-trifluoromethyl-4-aminophenol) was the only reductive metabolite identified through liquid chromatography-high-resolution mass spectrometry screening of liver extracts incubated with TFM and was targeted for electrochemical synthesis. After synthesis and purification, aTFM was used to develop a quantitative assay of the reductive metabolism of TFM through liquid chromatography and tandem mass spectrometry. The concentrations of aTFM were measured from TFM-treated cellular fractions, including cytosolic, nuclear, membrane, and mitochondrial protein extracts. Sea lamprey extracts produced the highest concentrations (500 ng/mL) of aTFM. In addition, sea lamprey and sturgeon cytosolic extracts showed concentrations of aTFM substantially higher than those of rainbow trout. However, other fractions of lake sturgeon extracts tend to show aTFM concentrations similar to those of rainbow trout but not with sea lamprey. These data suggest that the level of reductive metabolism of TFM may be associated with the sensitivities of the animals to this particular pesticide.

  20. Probing Protein 3D Structures and Conformational Changes Using Electrochemistry-Assisted Isotope Labeling Cross-Linking Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zheng, Qiuling; Zhang, Hao; Wu, Shiyong; Chen, Hao

    2016-05-01

    This study presents a new chemical cross-linking mass spectrometry (MS) method in combination with electrochemistry and isotope labeling strategy for probing both protein three-dimensional (3D) structures and conformational changes. For the former purpose, the target protein/protein complex is cross-linked with equal mole of premixed light and heavy isotope labeled cross-linkers carrying electrochemically reducible disulfide bonds (i.e., DSP-d0 and DSP-d8 in this study, DSP = dithiobis[succinimidyl propionate]), digested and then electrochemically reduced followed with online MS analysis. Cross-links can be quickly identified because of their reduced intensities upon electrolysis and the presence of doublet isotopic peak characteristics. In addition, electroreduction converts cross-links into linear peptides, facilitating MS/MS analysis to gain increased information about their sequences and modification sites. For the latter purpose of probing protein conformational changes, an altered procedure is adopted, in which the protein in two different conformations is cross-linked using DSP-d0 and DSP-d8 separately, and then the two protein samples are mixed in 1:1 molar ratio. The merged sample is subjected to digestion and electrochemical mass spectrometric analysis. In such a comparative cross-linking experiment, cross-links could still be rapidly recognized based on their responses to electrolysis. More importantly, the ion intensity ratios of light and heavy isotope labeled cross-links reveal the conformational changes of the protein, as exemplified by examining the effect of Ca2+ on calmodulin conformation alternation. This new cross-linking MS method is fast and would have high value in structural biology.

  1. The application of electrochemistry to pharmaceutical stability testing--comparison with in silico prediction and chemical forced degradation approaches.

    PubMed

    Torres, Susana; Brown, Roland; Szucs, Roman; Hawkins, Joel M; Zelesky, Todd; Scrivens, Garry; Pettman, Alan; Taylor, Mark R

    2015-11-10

    The aim of this study was to evaluate the use of electrochemistry to generate oxidative degradation products of a model pharmaceutical compound. The compound was oxidized at different potentials using an electrochemical flow-cell fitted with a glassy carbon working electrode, a Pd/H2 reference electrode and a titanium auxiliary electrode. The oxidative products formed were identified and structurally characterized by LC-ESI-MS/MS using a high resolution Q-TOF mass spectrometer. Results from electrochemical oxidation using electrolytes of different pH were compared to those from chemical oxidation and from accelerated stability studies. Additionally, oxidative degradation products predicted using an in silico commercially available software were compared to those obtained from the various experimental methods. The electrochemical approach proved to be useful as an oxidative stress test as all of the final oxidation products observed under accelerated stability studies could be generated; previously reported reactive intermediate species were not observed most likely because the electrochemical mechanism differs from the oxidative pathway followed under accelerated stability conditions. In comparison to chemical degradation tests electrochemical degradation has the advantage of being much faster and does not require the use of strong oxidizing agents. Moreover, it enables the study of different operating parameters in short periods of time and optimisation of the reaction conditions (pH and applied potential) to achieve different oxidative products mixtures. This technique may prove useful as a stress test condition for the generation of oxidative degradation products and may help accelerate structure elucidation and development of stability indicating analytical methods.

  2. Metabolite identification of a radiotracer by electrochemistry coupled to liquid chromatography with mass spectrometric and radioactivity detection.

    PubMed

    Baumann, Anne; Faust, Andreas; Law, Marylin P; Kuhlmann, Michael T; Kopka, Klaus; Schäfers, Michael; Karst, Uwe

    2011-07-01

    Radioligands, which specifically bind to a receptor or enzyme (target), enable molecular imaging of the target expression by positron emission tomography (PET). One very promising PET tracer is (S)-1-(4-(2-[(18)F]-fluoroethoxy)benzyl)-5-[1-(2-methoxymethylpyrrolidinyl)sulfonyl]isatin (isatin), a caspase-3 inhibitor, which has been developed at the University Hospital of Münster to image cell death (apoptosis). The translation of this novel tracer from preclinical evaluation to clinical examinations requires biodistribution studies, which characterize the pharmakodynamics and metabolic fate of the compound. This information is used to further optimize the radioligands and to interpret radioactive signals from tissues upon injection of the radioligand in vivo with respect to their specificity. The analysis of the metabolism of radioligands is hampered by the low amount of the compound being typically injected (nano/picomolar amount per injection). In the present study, electrochemistry (EC) is applied to elucidate the oxidative metabolism pathway of the radiotracer. Previous studies have demonstrated that EC can be utilized as a complementary tool to conventional in vitro approaches in drug metabolism studies. Thereby, potential oxidative metabolites of the isatin are determined by EC coupled to electrospray ionization mass spectrometry (EC/ESI-MS). Moreover, using EC/liquid chromatography (LC) and ESI-ion trap MS(n), structural elucidation of the oxidation products is performed. Comparatively to EC, in vitro metabolism studies with rat liver microsomes are conducted. Finally, the developed LC/ESI-MS method is applied to determine metabolites in body fluids and cell extracts from in vivo studies with the nonradioactive ((19)F) and radioactive isatin ((18)F). On the basis of the electrochemically generated oxidation products of the radioligand, the major radioactive metabolite occurring in vivo was successfully identified.

  3. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

    DOE PAGES

    Sundararaman, Ravishankar; Goddard, III, William A.; Arias, Tomas A.

    2017-03-16

    First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solvemore » the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Lastly, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.« less

  4. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

    NASA Astrophysics Data System (ADS)

    Sundararaman, Ravishankar; Goddard, William A.; Arias, Tomas A.

    2017-03-01

    First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solve the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Finally, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.

  5. ELECTROCHEMISTRY AND ON-CELL REFORMATION MODELING FOR SOLID OXIDE FUEL CELL STACKS

    SciTech Connect

    Recknagle, Kurtis P.; Jarboe, Daniel T.; Johnson, Kenneth I.; Korolev, Alexander; Khaleel, Mohammad A.; Singh, Prabhakar

    2007-01-16

    ABSTRACT Providing adequate and efficient cooling schemes for solid-oxide-fuel-cell (SOFC) stacks continues to be a challenge coincident with the development of larger, more powerful stacks. The endothermic steam-methane reformation reaction can provide cooling and improved system efficiency when performed directly on the electrochemically active anode. Rapid kinetics of the endothermic reaction typically causes a localized temperature depression on the anode near the fuel inlet. It is desirable to extend the endothermic effect over more of the cell area and mitigate the associated differences in temperature on the cell to alleviate subsequent thermal stresses. In this study, modeling tools validated for the prediction of fuel use, on-cell methane reforming, and the distribution of temperature within SOFC stacks, are employed to provide direction for modifying the catalytic activity of anode materials to control the methane conversion rate. Improvements in thermal management that can be achieved through on-cell reforming is predicted and discussed. Two operating scenarios are considered: one in which the methane fuel is fully pre-reformed, and another in which a substantial percentage of the methane is reformed on-cell. For the latter, a range of catalytic activity is considered and the predicted thermal effects on the cell are presented. Simulations of the cell electrochemical and thermal performance with and without on-cell reforming, including structural analyses, show a substantial decrease in thermal stresses for an on-cell reforming case with slowed methane conversion.

  6. Bipolar Electrochemistry for Concurrently Evaluating the Stability of Anode and Cathode Electrocatalysts and the Overall Cell Performance during Long-Term Water Electrolysis.

    PubMed

    Eßmann, Vera; Barwe, Stefan; Masa, Justus; Schuhmann, Wolfgang

    2016-09-06

    Electrochemical efficiency and stability are among the most important characteristics of electrocatalysts. These parameters are usually evaluated separately for the anodic and cathodic half-cell reactions in a three-electrode system or by measuring the overall cell voltage between the anode and cathode as a function of current or time. Here, we demonstrate how bipolar electrochemistry can be exploited to evaluate the efficiency of electrocatalysts for full electrochemical water splitting while simultaneously and independently monitoring the individual performance and stability of the half-cell electrocatalysts. Using a closed bipolar electrochemistry setup, all important parameters such as overvoltage, half-cell potential, and catalyst stability can be derived from a single galvanostatic experiment. In the proposed experiment, none of the half-reactions is limiting on the other, making it possible to precisely monitor the contribution of the individual half-cell reactions on the durability of the cell performance. The proposed approach was successfully employed to investigate the long-term performance of a bifunctional water splitting catalyst, specifically amorphous cobalt boride (Co2B), and the durability of the electrocatalyst at the anode and cathode during water electrolysis. Additionally, by periodically alternating the polarization applied to the bipolar electrode (BE) modified with a bifunctional oxygen electrocatalyst, it was possible to explicitly follow the contributions of the oxygen reduction (ORR) and the oxygen evolution (OER) half-reactions on the overall long-term durability of the bifunctional OER/ORR electrocatalyst.

  7. Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

    2015-10-01

    Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

  8. Hydrogen Electrochemistry in SiO2 Related to Breakdown of Gate Oxides

    NASA Astrophysics Data System (ADS)

    Bloechl, Peter

    2000-03-01

    Further scaling of semiconductor devices faces major difficulties due to the limited lifetime of the gate oxide, which will be scaled below 2 ~ nm within 5 years. Breakdown has been correlated with stress-induced leakage currents (SILC) induced by hydrogen. State-of-the-art electronic structure calculations of defects related to hydrogen and oxygen vacancies in SiO2 have been performed. The origin of the SILC is attributed to the hydrogen bridge, as the only stable defect allowing two-step tunneling below 3 ~eV. The result is confirmed by EDMR measurements. I argue that SILC is not the direct cause of SILC, but some related electrochemical process. Hydrogen reactions with SiO2 indicate the creation of charged coordination defects, which results in a pathway for hydrogen induced electromigration that potentially may be the cause of breakdown.

  9. Electrochemistry of mixed oxygen ion and electron conducting electrodes in solid electrolyte cells.

    PubMed

    Chueh, William C; Haile, Sossina M

    2012-01-01

    Mixed ion and electron conductors (MIECs) have garnered increased attention as active components in the electrodes of solid oxide electrolyzers (for electricity to fuel conversion) and especially of solid oxide fuel cells (for fuel to electricity conversion). Although much of the work in the literature is directed toward the understanding of oxygen electroreduction on the surfaces of MIECs, more recent studies also explore the role of these materials in fuel electrooxidation. In both cases, the rich chemical and electronic behaviors of MIECs imply a broad range of possible reaction pathways. We highlight the significant progress that has been made in elucidating these pathways through well-designed experimental and computational studies. At the macroscopic level, patterned electrode studies enable identification of active sites, whereas at the microscopic level, surface-sensitive techniques in combination with atomistic-level simulations are beginning to reveal the nature of the rate-determining step(s) and enable rational design of materials with enhanced activity.

  10. Vibrational properties of fractionally charged molecules and their relevance for molecular electronics and electrochemistry

    NASA Astrophysics Data System (ADS)

    Bâldea, Ioan

    2017-01-01

    Important insight into the charge transfer across interfaces can be gained in situations wherein, for given adsorbate and substrate species, the (fractional) charge state of the adsorbed molecules can be varied in a controlled way. Applied biases can continuously tune the charge of molecules embedded in nanojunctions and/or in electrochemical setups but information on the fractional charges of the corresponding partial oxidized/reduced states cannot be directly accessed in experiments. Here, we present theoretical results revealing that information on the fractional molecular charge can be obtained by monitoring molecular vibrational properties, which can be measured by means of surface enhanced Raman spectroscopy (SERS). To this aim, we performed DFT calculations for the benchmark 1,4-benzenedithiol molecule. The changes in the vibrational frequencies are considerably larger than those recently measured in combined transport-SERS studies on molecular junctions based on fullerene. We believe that this theoretical result is an encouraging message to experimentalists.

  11. Covalent dimers of 1,3-diphenylisobenzofuran for singlet fission: synthesis and electrochemistry.

    PubMed

    Akdag, Akin; Wahab, Abdul; Beran, Pavel; Rulíšek, Lubomír; Dron, Paul I; Ludvík, Jiří; Michl, Josef

    2015-01-02

    The synthesis of covalent dimers in which two 1,3-diphenylisobenzofuran units are connected through one phenyl substituent on each is reported. In three of the dimers, the subunits are linked directly, and in three others, they are linked via an alkane chain. A seventh new compound in which two 1,3-diphenylisobenzofuran units share a phenyl substituent is also described. These materials are needed for investigations of the singlet fission process, which promises to increase the efficiency of solar cells. The electrochemical oxidation and reduction of the monomer, two previously known dimers, and the seven new compounds have been examined, and reversible redox potentials have been compared with results obtained from density functional theory. Although the overall agreement is satisfactory, some discrepancies are noted and discussed.

  12. Se adlattices formed on Au(100), studies by LEED, AES, STM and electrochemistry

    NASA Astrophysics Data System (ADS)

    Huang, Baoming M.; Lister, Tedd E.; Stickney, John L.

    1997-12-01

    Ordered selenium atomic layers have been formed electrochemically on Au(100) at a series of coverages. Cyclic voltammetry and coulometry were used to study the deposition process, and to determine the corresponding coverages of a number of Se structures. Structures, with Se coverages of 0.25, 0.33, 0.5, and 0.89 monolayers, were identified using ultra high vacuum — electrochemical techniques as well as scanning tunneling microscopy. The corresponding unit cells of those structures were: p(2 × 2), (2 × √10), c(2 × 2), and a mostly (3 × √10), composed of close-packed Se 8 rings. Pit formation, associated with the formation of the densely packed Se 8 ring structure, was observed. They are reminiscent of pits observed in self-assembled monolayers of alkane thiols on Au surfaces. The pits disappeared as the structure, composed of Se rings, was converted to lower coverage structures, such as the 0.25 monolayer p(2 × 2), via anodic stripping. Se atomic layers were formed electrochemically in three ways: direct reduction from a HSeO -3 solution; anodic stripping of previously formed bulk Se; or cathodic stripping of previously formed bulk Se. All three methods resulted in equivalent atomic layer structures on the Au(100) surface, but with some variation in the homogeneity and distribution of particular structures.

  13. The Hydrothermal Synthesis and Electrochemistry of Oxyfluorides and Fluoro-bronzes for Lithium and Multivalent Battery Cathodes

    NASA Astrophysics Data System (ADS)

    Incorvati, Jared T.

    experiments on the electrochemistry of organic materials, a new phenomenon in contact electrification is described wherein insulators charge with one polarity before becoming uncharged then finally charging with the opposite polarity. The likelihood of contact charging insulators to undergo polarity reversal is linked to the difference in the materials' Young's moduli. X-ray photoelectron spectroscopy, atomic force microscopy, and Kelvin force microscopy surface studies reveal that exchanged materials act as charge carriers in these systems.

  14. In-Situ TEM Electrochemistry of Individual Nanowire and Nanoparticle Electrodes in a Li-Ion Cell

    NASA Astrophysics Data System (ADS)

    Huang, Jianyu

    2012-02-01

    Recently, we created the first Li-ion electrochemical cell inside a transmission electron microscope (TEM) and observed, in real time with atomic scale resolution, the lithiation/delithiation processes. This experiment opened the door for a suite of experimental studies involving in-situ TEM characterization of Li-ion battery materials. In this presentation, I'll first review our latest progress of using the in-situ electrochemical cell setup inside the TEM to reveal the intrinsic electrochemistry of several high energy density anode materials such as SnO2, ZnO, Si, Ge, Al nanowires, Si nanoparticles, carbon nanotubes, and graphene. Several electrochemical mechanisms were observed and characterized in real-time, including lithiation induced stress, volume changes, phase transformations, pulverization, cracking, embrittlement, and mechanical failure in anode materials. These results indicate the strong material, size and crystallographic orientation dependent electrochemical behavior and degradation mechanisms that occur in Li-ion battery anodes. In the future, we will need further advancements in in-situ characterization for understanding important processes in Li-ion batteries. For example, liquid cells are required in order to examine the electrochemical reactions between battery materials and the standard battery electrolytes, which are ethylene carbonate-based. Furthermore, in-situ studies need to be correlated with electrochemical studies performed on bulk electrodes. I will present a comparison between our in-situ results and electrochemical studies on conventional battery electrodes and highlight how in-situ studies can have important impact on the design of Li-ion batteries. Finally I will discuss outstanding challenging issues and opportunities in the field of Li-ion battery research. [4pt] References: Science 330, 1515 (2010); 330, 1485 (2010); Nano Lett. Doi: 10.1021/nl200412p, 10.1021/nl2024118, 10.1021/nl201684d, 10.1021/nl202088h, ACS Nano, doi: 10

  15. 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.

  16. Single-Molecule Electrochemistry on a Porous Silica-Coated Electrode.

    PubMed

    Lu, Jin; Fan, Yunshan; Howard, Marco D; Vaughan, Joshua C; Zhang, Bo

    2017-03-01

    Here we report the direct observation and quantitative analysis of single redox events on a modified indium-tin oxide (ITO) electrode. The key in the observation of single redox events are the use of a fluorogenic redox species and the nanoconfinement and hindered redox diffusion inside 3-nm-diameter silica nanochannels. A simple electrochemical process was used to grow an ultrathin silica film (∼100 nm) consisting of highly ordered parallel nanochannels exposing the electrode surface from the bottom. The electrode-supported 3-nm-diameter nanochannels temporally trap fluorescent resorufin molecules resulting in hindered molecular diffusion in the vicinity of the electrode surface. Adsorption, desorption, and heterogeneous redox events of individual resorufin molecules can be studied using total-internal reflection fluorescence (TIRF). The rate constants of adsorption and desorption processes of resorufin were characterized from single-molecule analysis to be (1.73 ± 0.08) × 10(-4) cm·s(-1) and 15.71 ± 0.76 s(-1), respectively. The redox events of resorufin to the non-fluorescent dihydroresorufin were investigated by analyzing the change in surface population of single resorufin molecules with applied potential. The scan-rate-dependent molecular counting results (single-molecule fluorescence voltammetry) indicated a surface-controlled electrochemical kinetics of the resorufin reduction on the modified ITO electrode. This study demonstrates the great potential of mesoporous silica as a useful modification scheme for studying single redox events on a variety of transparent substrates such as ITO electrodes and gold or carbon film coated glass electrodes. The ability to electrochemically grow and transfer mesoporous silica films onto other substrates makes them an attractive material for future studies in spatial heterogeneity of electrocatalytic surfaces.

  17. Etude de lasers a fibre emettant a 480 nm et du phenomene de coloration dans la fibre de ZBLAN dopee au thulium

    NASA Astrophysics Data System (ADS)

    Laperle, Pierre

    Cet ouvrage porte sur l'etude experimentale et theorique du laser a fibre de ZBLAN dopee au thulium pompe a 1112 nm par un laser Nd:YAG et emettant a 480 nm, ainsi que du phenomene de coloration causant la photodegradation du laser a fibre. Le rendement du laser a fibre depend de l'efficacite de la conversion de photons infrarouges en photons visibles par un mecanisme d'excitation en palier des ions trivalent thulium (Tm3+). Toutefois, cette efficacite est reduite par les transferts d'energie entre les ions Tm3+. De plus, le gain net est limite par l'absorption induite a la longueur d'onde laser pendant le pompage de la fibre a 1112 nm. Cette absorption induite s'avere etre le probleme le plus important a surmonter pour le developpement d'un laser a fibre a 480 nm qui soit stable et de haute puissance. La spectroscopie de l'ion Tm3+ dans la fibre de ZBLAN a ete realisee afin de determiner experimentalement les parametres essentiels a la modelisation theorique du laser a fibre. Les sections efficaces d'absorption et d'emission de l'ion Tm3+ ont ete calculees a partir des equations de Fuchtbauer-Ladenburg et des spectres d'intensite d'absorption et d'emission spontanee mesures experimentalement par excitation selective. Cette methode d'excitation a permis de resoudre spectralement certaines des transitions d'absorption mal connues dues a la difficulte de mesurer celles-ci de facon directe. L'identification des transferts d'energie (relaxation croisee et excitation cooperative en palier) dominants entre ions Tm 3+ a ete faite en comparant la probabilite d'interaction dipole-dipole electriques entre une paire d'ion Tm 3+. Les taux de transferts d'energie, quant a eux, ont ete mesures par excitation selective et la mesure du temps de vie des niveaux d'energie de l'ion Tm3+. La sensibilite de la fibre de ZBLAN a la lumiere et a la chaleur est decrite habituellement par leurs effets sur la transparence de la fibre, par exemple, photonoircissement, photoblanchiment et

  18. Electrochemistry and catalytic properties for dioxygen reduction using ferrocene-substituted cobalt porphyrins.

    PubMed

    Sun, Bin; Ou, Zhongping; Meng, Deying; Fang, Yuanyuan; Song, Yang; Zhu, Weihua; Solntsev, Pavlo V; Nemykin, Victor N; Kadish, Karl M

    2014-08-18

    Cobalt porphyrins having 0-4 meso-substituted ferrocenyl groups were synthesized and examined as to their electrochemical properties in N,N'-dimethylformamide (DMF) containing 0.1 M tetra-n-butylammonium perchlorate as a supporting electrolyte. The examined compounds are represented as (Fc)n(CH3Ph)(4-n)PorCo, where Por is a dianion of the substituted porphyrin, Fc and CH3Ph represent ferrocenyl and/or p-CH3C6H4 groups linked at the four meso-positions of the macrocycle, and n varies from 0 to 4. Each porphyrin undergoes two reversible one-electron reductions and two to six one-electron oxidations in DMF, with the exact number depending upon the number of Fc groups on the compound. The first electron addition is metal-centered to generate a Co(I) porphyrin. The second is porphyrin ring-centered and leads to formation of a Co(I) π-anion radical. The first oxidation of each Co(II) porphyrin is metal-centered to generate a Co(III) derivative under the given solution conditions. Each ferrocenyl substituent can also be oxidized by one electron, and this occurs at more positive potentials. Each compound was investigated as a catalyst for the electoreduction of dioxygen when adsorbed on a graphite electrode in 1.0 M HClO4. The number of electrons transferred (n) during the catalytic reduction was 2.0 for the three ferrocenyl substituted compounds, consistent with only H2O2 being produced as a product of the reaction. Most monomeric cobalt porphyrins exhibit n values between 2.6 and 3.1 under the same solution conditions, giving a mixture of H2O and H2O2 as a reduction product, although some monomeric porphyrins can give an n value of 4.0. Our results in the current study indicate that appending ferrocene groups directly to the meso positions of a porphyrin macrocycle will increase the selectivity of the oxygen reduction, resulting in formation of only H2O2 as a reaction product. This selectivity of the electrocatalytic oxygen reduction reaction is explained on the basis

  19. Etude de l'influence de la temperature et de l'humidite sur les proprietes mecaniques en traction des fibres de chanvre et de coco

    NASA Astrophysics Data System (ADS)

    Ho Thi, Thu Nga

    L'objectif de cette etude fut d'etablir l'effet de l'humidite et de la temperature sur la resistance en traction et le module elastique des fibres de chanvre et de coco. Deux etudes ont ete realisees afin d'atteindre cet objectif. La premiere vise l'absorption de l'humidite dans ces fibres en exposition dans l'air (de 0%RH a 80%RH) ainsi que l'absorption de l'eau dans ces fibres immergees dans l'eau aux differentes temperatures. La deuxieme consiste a mesurer la resistance en traction et le module elastique de ces fibres sous differentes conditions d'humidite et de temperature. En basant sur les resultats experimentaux obtenus, les methodes semi empiriques et de reseaux de neurones ont ete utilisees pour but de predire les proprietes en traction (resistance et module d'elasticite) des fibres de chanvre et de coco sous l'influence de l'humidite et de la temperature.

  20. 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 (TiO2) 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 TiO2 nanoparticles and employed for obtaining a suitable solid surface to enzyme attachment. The glucose oxidase (GOD) was irreversibly loaded on the GC/GO/TiO2-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/TiO2-OISL can catalyze the electroreduction and electrooxidation of hydrogen peroxide. The GC/GO/TiO2-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.

  1. Electrochemistry at a Metal Nanoparticle on a Tunneling Film: A Steady-State Model of Current Densities at a Tunneling Ultramicroelectrode.

    PubMed

    Hill, Caleb M; Kim, Jiyeon; Bard, Allen J

    2015-09-09

    Here, a new methodology is proposed for treating electrochemical current densities in metal-insulator-metal nanoparticle (M-I-MNP) systems. The described model provides broad, practical insights about MNP-mediated electron transfer to redox species in solution, where electron transfer from the underlying electrode to a MNP via tunneling and heterogeneous electron transfer from the MNP to redox species in solution are treated as sequential steps. Tunneling is treated through an adaptation of the Simmons model of tunneling in metal-insulator-metal structures, and explicit equations are provided for tunneling currents, which demonstrate the effect of various experimental parameters, such as insulator thickness and MNP size. Overall, a general approach is demonstrated for determining experimental conditions where tunneling will have a measurable impact on the electrochemistry of M-I-MNP systems.

  2. End-of-Discharge and End-of-Life Prediction in Lithium-Ion Batteries with Electrochemistry-Based Aging Models

    NASA Technical Reports Server (NTRS)

    Daigle, Matthew; Kulkarni, Chetan S.

    2016-01-01

    As batteries become increasingly prevalent in complex systems such as aircraft and electric cars, monitoring and predicting battery state of charge and state of health becomes critical. In order to accurately predict the remaining battery power to support system operations for informed operational decision-making, age-dependent changes in dynamics must be accounted for. Using an electrochemistry-based model, we investigate how key parameters of the battery change as aging occurs, and develop models to describe aging through these key parameters. Using these models, we demonstrate how we can (i) accurately predict end-of-discharge for aged batteries, and (ii) predict the end-of-life of a battery as a function of anticipated usage. The approach is validated through an experimental set of randomized discharge profiles.

  3. Ferrocene-based sulfonyl dihydropyrazole derivatives: Synthesis, structure, electrochemistry and effect on thermal decomposition of NH4ClO4

    NASA Astrophysics Data System (ADS)

    Zhuo, Ji-Bin; Li, Heng-Dong; Lin, Cai-Xia; Xie, Li-Li; Bai, Sha; Yuan, Yao-Feng

    2014-06-01

    Three ferrocene-based sulfonyl-substituted dihydropyrazoles 3a-c have been synthesized, from the corresponding α,β-unsaturated diketones, and fully characterized. The crystal structures of 3a-c have been confirmed by X-ray crystallography, and electrochemistry behaviors of 3a-c have been examined by cyclic voltammetry (CV). Representatively, the mechanism of the electron transfer in redox process of 3a has been verified by density functional theory (DFT) calculation. It has been found that the activity of catalytic decomposition of ammonium perchlorate (AP) is significantly lowered (by 62.9-104.7 °C) with an addition of 3a-c. We expect that the ferrocene-based sulfonyl dihydropyrazole derivatives would have a great value in burning rate catalyst as composite solid propellants.

  4. Depth probing of the hydride formation process in thin Pd films by combined electrochemistry and fiber optics-based in situ UV/vis spectroscopy.

    PubMed

    Wickman, Björn; Fredriksson, Mattias; Feng, Ligang; Lindahl, Niklas; Hagberg, Johan; Langhammer, Christoph

    2015-07-15

    We demonstrate a flexible combined electrochemistry and fiber optics-based in situ UV/vis spectroscopy setup to gain insight into the depth evolution of electrochemical hydride and oxide formation in Pd films with thicknesses of 20 and 100 nm. The thicknesses of our model systems are chosen such that the films are thinner or significantly thicker than the optical skin depth of Pd to create two distinctly different situations. Low power white light is irradiated on the sample and analyzed in three different configurations; transmittance through, and, reflectance from the front and the back side of the film. The obtained optical sensitivities correspond to fractions of a monolayer of adsorbed or absorbed hydrogen (H) and oxygen (O) on Pd. Moreover, a combined simultaneous readout obtained from the different optical measurement configurations provides mechanistic insights into the depth-evolution of the studied hydrogenation and oxidation processes.

  5. Type I collagen-mediated synthesis of noble metallic nanoparticles networks and the applications in Surface-Enhanced Raman Scattering and electrochemistry.

    PubMed

    Sun, Yujing; Sun, Lanlan; Zhang, Baohua; Xu, Fugang; Liu, Zhelin; Guo, Cunlan; Zhang, Yue; Li, Zhuang

    2009-08-15

    In this paper, we demonstrated an effective environmentally friendly synthesis route to prepare noble metallic (Au, Ag, Pt and Pd) nanoparticles (NPs) networks mediated by type I collagen in the absence of any seeds or surfactants. In the reactions, type I collagen served as stabilizing agent and assembly template for the synthesized metallic NPs. The hydrophobic interaction between collagen and mica interface as well as the hydrogen bonds between inter- and intra-collagen molecules play important roles in the formation of collagen-metallic NPs networks. The noble metallic NPs networks have many advantages in the applications of Surface-Enhanced Raman Scattering (SERS) and electrochemistry detection. Typically, the as-prepared Ag NPs networks reveal great Raman enhancement activity for 4-ATP, and can even be used to detect low concentration of DNA base, adenine, without any label step. Furthermore, the cyclic voltammograms showed Pt NPs networks have good electrocatalytic ability for the reduction of O(2).

  6. Analysis of cysteine-containing proteins using precolumn derivatization with N-(2-ferroceneethyl)maleimide and liquid chromatography/electrochemistry/mass spectrometry.

    PubMed

    Seiwert, Bettina; Karst, Uwe

    2007-08-01

    N-(2-ferroceneethyl)maleimide (FEM) is introduced as an electroactive derivatizing agent for thiol functionalities in proteins. Using appropriate reaction conditions, the derivatization is completed within five minutes and no unspecific labeling of free amino functions is observed. Liquid chromatography/electrochemistry/mass spectrometry was used to detect the reaction products. The reagent is a useful tool for determining the number of free thiol groups or the total number of free and disulfide-bound thiol groups in proteins. The electrochemical cell provides additional information, because the increase in mass spectrometric response upon electrochemical oxidation of the neutral ferrocene to the charged ferrocinium groups is monitored. The method was successfully applied to the analysis of native proteins and their tryptic digests.

  7. Li/Ag2VO2PO4 batteries: the roles of composite electrode constituents on electrochemistry

    SciTech Connect

    Bock, David C.; Bruck, Andrea M.; Pelliccione, Christopher J.; Zhang, Yiman; Takeuchi, Kenneth J.; Marschilok, Amy C.; Takeuchi, Esther S.

    2016-11-01

    In this study, we utilize silver vanadium phosphorous oxide, Ag2VO2PO4, as a model system to systematically study the impact of the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Notably, although highly resistive, this bimetallic cathode can be discharged as a pure electroactive material in the absence of a conductive additive as it generates an in situ conductive matrix via a reduction displacement reaction resulting in the formation of silver metal nanoparticles. Also, three different electrode compositions were investigated: Ag2VO2PO4 only, Ag2VO2PO44 with binder, and Ag2VO2PO4 with binder and carbon. Constant current discharge, pulse testing and impedance spectroscopy measurements were used to characterize the electrochemical properties of the electrodes as a function of depth of discharge. In situ EDXRD was used to spatially resolve the discharge progression within the cathode by following the formation of Ag0. Ex situ XRD and EXAFS modeling were used to quantify the amount of Ag0 formed. Results indicate that the metal center reduced (V5+ or Ag+) was highly dependent on composite composition (presence of PTFE, carbon), depth of discharge (Ag0 nanoparticle formation), and spatial location within the cathode. The addition of a binder was found to increase cell polarization, and the percolation network provided by the carbon in the presence of PTFE was further increased with reduction and formation of Ag0. Lastly, this study provides insight into the factors controlling the electrochemistry of resistive active materials in composite electrodes.

  8. Characterization of the primary electron donor of photosystem I, P700, by electrochemistry and Fourier transform infrared (FTIR) difference spectroscopy

    NASA Astrophysics Data System (ADS)

    Hamacher, E.; Kruip, J.; Rögner, M.; Mäntele, W.

    1996-01-01

    The redox reactions of P700, the primary electron donor of photosystem I (PS I), have been analyzed by electrochemistry and Fourier transform infrared (FTIR) spectroscopy in two different preparations from the cyanobacterium Synechocystis PCC 6803 yielding monomeric and trimeric PS I complexes, respectively. Reversible and quantitative oxidation and rereduction of P700 has been achieved at surface-modified electrodes in an optically and infrared transparent thin-layer electrochemical (OTTLE) cell. The midpoint potential ( Em = +260 ± 10 mV vs. Ag/AgCl/3 M KCl) determined from these titrations, either by monitoring the electrochemically-induced oxidation/reduction of the primary electron donor P700 at 700 nm or by monitoring the amplitude of the flash-induced absorbance change at 707 nm as a function of the applied potential, agree between monomeric and trimeric PS I, demonstrating that protein-protein contact has very little impact on the redox properties of P700. Using electrochemical oxidation and rereduction, the vibrational IR difference spectra P700 ·+ - P700 could be generated. In the 1800-1200 cm -1 spectral region, highly structured IR difference spectra were obtained. The IR difference bands titrate in unison and are fully reversible upon application of a reducing potential. The midpoint potential measured by titration of the absorbance difference of two prominent bands, at 1714 and 1696 cm -1( Em = +260 ± 10 mV) corresponds to the values determined by titration of the electronic transition of P700. In contrast to previously obtained FTIR difference spectra for light-induced charge separation (E. Nabedryk, M. Leonhard, W. Mäntele and J. Breton, Biochemistry, 29 (1990) 3242; G. MacDonald, K.A. Bixby and B.A. Barry, Proc. Natl. Acad. Sci. USA, 90 (1993) 11024) which include contributions from the primary electron donor and the acceptor side, the electrochemical generated FTIR difference spectra exclusively reflect the molecular changes at P700 and its

  9. Directing 101.

    ERIC Educational Resources Information Center

    Pintoff, Ernest

    Providing an introduction to anyone considering directing as a field of study or career, this book takes a broad look at the process of directing and encourages students and professionals alike to look outside of the movie industry for inspiration. Chapters in the book discuss selecting and acquiring material; budgeting and financing; casting and…

  10. Directing 101.

    ERIC Educational Resources Information Center

    Pintoff, Ernest

    Providing an introduction to anyone considering directing as a field of study or career, this book takes a broad look at the process of directing and encourages students and professionals alike to look outside of the movie industry for inspiration. Chapters in the book discuss selecting and acquiring material; budgeting and financing; casting and…

  11. Combine electrochemistry with photocatalysis

    SciTech Connect

    Vinodgopal, K.; Kamat, P.V.

    1996-04-01

    Because a substantial percentage of colorant is lost during the dyeing process, remediation efforts have largely been focused on removing these dyes from the wastewater effluents of textile mills and other industrial colorant users. Incomplete decolorization of the effluent before discharge shifts the burden of treatment downstream. In publicly owned water treatment facilities, these dyes often end up as sludges that are dewatered and eventually deposited in landfills. There is a substantial economic impetus to develop a flow reactor to be used onstream by mills to treat colorant effluent and recycle the water. The authors have developed a photocatalytic approach using semiconductors for degrading several azo dyes. They recently found that deposition of semiconductor nanoclusters on a conducting glass surface provides a convenient way to manipulate the photocatalytic reaction by electrochemical methods. The thin semiconductor particulate film can be used as a photosensitive electrode in an electrochemical cell. The paper describes electrode preparation, the photoelectrochemical properties of TiO{sub 2} and SnO{sub 2}, reaction mechanism, and composite semiconductor films.

  12. Electrochemistry on Mars.

    PubMed

    West, S J; Frant, M S; Wen, X; Geis, R; Herdan, J; Gillette, T; Hecht, M H; Schubert, W; Grannan, S; Kounaves, S P

    1999-10-01

    Researchers describe research design and equipment for electrochemical analysis of Martian soil. The Wet Chemistry Laboratory (WCL) was designed for the Mars Surveyor 2001 Lander by the Mars Environmental Compatibility Assessment (MECA) team. The WCL consists of four beakers, each containing an integral array of electrochemical sensors. In addition to describing WCL design, the article discusses WCL sensor selection and design, analytical goals of the MECA experiments, expected composition of the Martian regolith, survival and performance testing, and reference electrode selection. The description of the research design describes experiment initiation, warm-up, leaching solution, calibration, sampling, analysis, reagent addition, and data analysis.

  13. Surface Electrochemistry of Metals

    DTIC Science & Technology

    1993-04-30

    171.** Auger Electron Angular Distributions from Underpotentially Deposited Ag Monolayers and Films at Pt(I 11) Pretreated with Iodine. Charles A...chemical vapor deposition (RTCVD), in which the heated Si(100) surface was carbonized with propane. Auger emission angular distributions were measured

  14. Electrochemistry for Energy Conversion

    NASA Astrophysics Data System (ADS)

    O'Hayre, Ryan

    2010-10-01

    Imagine a laptop computer that runs for 30 hours on a single charge. Imagine a world where you plug your house into your car and power lines are a distant memory. These dreams motivate today's fuel cell research. While some dreams (like powering your home with your fuel cell car) may be distant, others (like a 30-hour fuel cell laptop) may be closer than you think. If you are curious about fuel cells---how they work, when you might start seeing them in your daily life--- this talk is for you. Learn about the state-of-the art in fuel cells, and where the technology is likely to be headed in the next 20 years. You'll also be treated to several ``behind-the scenes'' glimpses of cutting-edge research projects under development in the Renewable Energy Materials Center at the Colorado School of Mines--- projects like an ``ionic transistor'' that works with protons instead of electrons, and a special ceramic membrane material that enables the ``uphill'' diffusion of steam. Associate Professor Ryan O'Hayre's laboratory at the Colorado School of Mines develops new materials and devices to enable alternative energy technologies including fuel cells and solar cells. Prof. O'Hayre and his students collaborate with the Colorado Fuel Cell Center, the Colorado Center for Advanced Ceramics, the Renewable Energy Materials Science and Engineering Center, and the National Renewable Energy Laboratory.[4pt] In collaboration with Ann Deml, Jianhua Tong, Svitlana Pylypenko, Archana Subramaniyan, Micahael Sanders, Jason Fish, Annette Bunge, Colorado School of Mines.

  15. Modern aspects of electrochemistry

    SciTech Connect

    White, R.E.; Bockris, J.O'M.; Conway, B.E.

    1983-01-01

    This book focuses on topics at the forefront of electrochemical research. Splitting water by electrolysis; splitting water by visible light; the recent development of lithium batteries; theoretical approaches to intercalation; and fundamental concepts of electrode kinetics, particularly as applied to semiconductors are discussed. It is recommended for electrochemists, physical chemists, corrosion scientists, and those working in the fields of analytical chemistry, surface and colloid science, materials science, electrical engineering, and chemical engineering.

  16. Modern aspects of electrochemistry

    SciTech Connect

    Bockris, J.M.; Conway, B.E.; White, R.E.

    1986-01-01

    This book presents information on the following topics: perspectives in electrochemical physics; modern state of double layer study of solid metals; photoelectrolysis and photoelectrochemical catalysis; electron transfer reactions on oxide-covered metal electrodes; and interfacial electrostatics and electrodynamics in disperse systems.

  17. Electrochemistry of Metal Surfaces

    DTIC Science & Technology

    1990-06-30

    1-butene (BTE), 1-pentene (PTE), l-hexene (HXE), 1-- octene (OCE) and l--decene (DCE). Vibrational spectra of the adsorbed layers were obtained by use...Surface Sci., 92, 617 (1980). 39. Electrochemical Hydrogenation of Ethylene at Well-Defined Pt(100) and Pt(111) Surfaces. Arthur T. Hubbard, Mark A...Surf Sci., 147, 241 (1984). 75. A Comparison of Gas Phase and Electrochemical Hydrogenation of Ethylene at ** Platinum Surfaces. Andrzej Wieckowski

  18. Nanomaterials in Electrochemistry

    DTIC Science & Technology

    2007-11-02

    feed solution is 1 mM in KCI and 0.5 mM in the cationic dye methylene blue , and the receiver solution is 1 mM KCI, the initially-colorless receiver...have interesting optical properties (20-22). For example, suspensions of nanoscopic Au particles can be pink, purple or blue depending on the...Au Nanotube Membranes (19). The pores in a commercially available polycarbonate filtration membrane (Poretics) were used as templates to form the

  19. Direct seeding

    Treesearch

    Richard M. Godman; G. A. Mattson

    1992-01-01

    At present, direct seeding of hardwoods in the Lake States is more of a supplemental than a primary means of artificial regeneration. Direct seeding may be used to augment a poor seed crop or increase the proportion of a preferred species. In the future, it will no doubt play a bigger role-in anticipation of this we need to collect and store the amounts of seed needed...

  20. Chromosomal mapping of human genes by radioactive hybridization of cDNAs to Centre d'Etude du Polymorphisme humain high density gridded filter sets.

    PubMed

    Claas, A; Savelyeva, L; Pillmann, A; Schwab, M

    2000-08-01

    Chromosomal assignment of human transcribed sequences has been done mainly by high throughput genome analysis in specialized genome centres and, in a more classical fashion, by fluorescence in-site hybridization (FISH) analysis. Not every laboratory has the ability to map cDNAs by FISH analysis. We here report a rapid mapping approach that is based on the hybridization of cDNA probes to high density gridded Centre d'Etude du Polymorphisme Humain filters followed by subsequent computational analysis by database searches in the internet. Not only transcribed sequences but also genomic DNA could be subjected to this mapping approach. The presented approach allows to map human transcribed and genomic DNAs within 1-3 days and with a high level of resolution that will constantly increase in line with the incorporation of data deriving from high throughput genome mapping.

  1. Randomized control trial for the assessment of the anti-albuminuric effects of topiroxostat in hyperuricemic patients with diabetic nephropathy (the ETUDE study).

    PubMed

    Kato, Sawako; Ando, Masahiko; Mizukoshi, Toshihiro; Nagata, Takanobu; Katsuno, Takayuki; Kosugi, Tomoki; Tsuboi, Naotake; Maruyama, Shoichi

    2016-05-01

    Proteinuria is an established risk factor for diabetic nephropathy. Recent studies indicate that some xanthine oxidase inhibitors have a renoprotective effect. The aim of this study was to assess whether topiroxostat reduces albuminuria in hyperuricemic patients with diabetic nephropathy and overt proteinuria. The ETUDE study is an ongoing 24-week, multicenter, open-label, randomized (1:1), parallel group study involving hyperuricemic patients with diabetic nephropathy (estimated glomerular filtration rate [eGFR] ≥ 20 mL/min/1.73 m(2)) and overt proteinuria (0.3 ≤ urine protein to creatinine ratio (UPCR) < 3.5 g/g Cr). Patients are randomly assigned to high dose (topiroxostat 160 mg daily) or low dose (topiroxostat 40 mg daily) on top of standard of care. The primary endpoint is the change in albuminuria indicated by urine albumin-to-creatinine ratio after 24 treated weeks relative to the baseline values. This trial was registered at the Japanese University Hospital Medical Information Network Clinical Trials Registry (UMIN-CTR: UMIN 000015403). The background, rationale, and study design of this trial are presented here. Seventy-six patients from four registered facilities have already been enrolled and received at least one dose of topiroxostat. This trial will end in 2017. The ETUDE trial is the first randomized controlled study of topiroxostat in hyperuricemic patients with diabetic nephropathy and overt proteinuria. We will clarify the pleiotropic function of topiroxostat including an anti-albumiuric effect as well as its effects on safely decreasing serum uric acid levels.

  2. Etude numerique et experimentale de la reponse vibro-acoustique des structures raidies a des excitations aeriennes et solidiennes

    NASA Astrophysics Data System (ADS)

    Mejdi, Abderrazak

    compte. Les modeles developpes ont permis de conduire plusieurs etudes parametriques sur les proprietes vibro-acoustiques des structures d'avions facilitant ainsi la tache des concepteurs. Dans le cadre de cette these, un article a ete publie dans le Journal of Sound and Vibration et trois autres soumis, respectivement aux Journal of Acoustical Society of America, International Journal of Solid Mechanics et au Journal of Sound and Vibration Mots cles : structures raidies, composites, vibro-acoustique, perte par transmission.

  3. Direct Instruction.

    ERIC Educational Resources Information Center

    Education Commission of the States, Denver, CO.

    This paper provides an overview of Direct Instruction, an intensive instructional method for grades K-6 based on the theory that learning can be greatly accelerated if instructional presentations are clear, rule out likely misinterpretations and facilitate generalizations. Over 50 instructional programs have been developed based on this…

  4. Etude par spectroscopie vibrationnelle des niobates de sodium et d'argent de structure perovskite

    NASA Astrophysics Data System (ADS)

    Husson, E.; Repelin, Y.

    Infrared and Raman spectra of the niobates NaNbO 3 and AgNbO 3 of perovskite structure are analysed. An assignment of the frequencies is proposed. The influence of the antiferroelectric direction upon the NbO bonds is shown, as the influence of the A cation upon the AO and NbO bonds.

  5. Electrochemistry-mass spectrometry for in-vitro determination of selected chemotherapeutics and their electrochemical products in comparison to in-vivo approach.

    PubMed

    Szultka-Mlynska, Malgorzata; Buszewski, Boguslaw

    2016-11-01

    Chemotherapeutics are among the most frequently prescribed medications in modern medicine. They are widely prescribed; however, problems with organisms developing resistance to these drugs means that their efficacy may be lost, so care should be taken to avoid unnecessary prescription. It is therefore of great interest to study the detailed metabolism of these biologically active compounds. This study aimed at developing an efficient analytical protocol for the determination of in-vitro electrochemical products of selected antibiotic drugs (amoxicillin, cefotaxime, fluconazole, linezolid, metronidazole and moxifloxacin). Combination of electrochemistry (EC) and mass spectrometry (MS) was applied for the in-vitro determination of the studied antibiotics and their electrochemical products. To identify the structure of the detected electrochemical products, MS/MS experiments were performed. This was one of the first applications of the EC system for generation of electrochemical products produced from antibiotic drugs. Adjustment of appropriate conditions and such parameters as the potential value, mobile phase (pH), working electrode and temperature had significant influence on electrochemical simulations and the creation of selected derivatives. Consequently, several working electrodes were evaluated for this purpose. In most of the studied cases, mainly two types of products were observed. One corresponded to an increase in mass by 14Da, which can be explained by a process consisting of oxidation (+16 m/z) and dehydrogenation (-2 m/z); The second in turn showed mass reduction by 14Da, which can be attributed to the loss of -CH2 as a result of N-demethylation. The performed experiments consisted of two stages: electrochemical oxidation of the analyzed samples (phase I of metabolic transformation), and addition of glutathione (GSH) for follow-up reactions (phase II conjunction). The electrochemical results were compared to in-vivo experiments by analyzing urine

  6. Coupled optical absorption, charge carrier separation, and surface electrochemistry in surface disordered/hydrogenated TiO2 for enhanced PEC water splitting reaction.

    PubMed

    Behara, Dilip Kumar; Ummireddi, Ashok Kumar; Aragonda, Vidyasagar; Gupta, Prashant Kumar; Pala, Raj Ganesh S; Sivakumar, Sri

    2016-03-28

    The central governing factors that influence the efficiency of photoelectrochemical (PEC) water splitting reaction are photon absorption, effective charge-carrier separation, and surface electrochemistry. Attempts to improve one of the three factors may debilitate other factors and we explore such issues in hydrogenated TiO2, wherein a significant increase in optical absorption has not resulted in a significant increase in PEC performance, which we attribute to the enhanced recombination rate due to the formation of amorphization/disorderness in the bulk during the hydrogenation process. To this end, we report a methodology to increase the charge-carrier separation with enhanced optical absorption of hydrogenated TiO2. Current methodology involves hydrogenation of non-metal (N and S) doped TiO2 which comprises (1) lowering of the band gap through shifting of the valence band via less electronegative non-metal N, S-doping, (2) lowering of the conduction band level and the band gap via formation of the Ti(3+) state and oxygen vacancies by hydrogenation, and (3) material processing to obtain a disordered surface structure which favors higher electrocatalytic (EC) activity. This design strategy yields enhanced PEC activity (%ABPE = 0.38) for the N-S co-doped TiO2 sample hydrogenated at 800 °C for 24 h over possible combinations of N-S co-doped TiO2 samples hydrogenated at 500 °C/24 h, 650 °C/24 h and 800 °C/72 h. This suggests that hydrogenation at lower temperatures does not result in much increase in optical absorption and prolonged hydrogenation results in an increase in optical absorption but a decrease in charge carrier separation by forming disorderness/oxygen vacancies in the bulk. Furthermore, the difference in double layer capacitance (C(dl)) calculated from electrochemical impedance spectroscopy (EIS) measurements of these samples reflects the change in the electrochemical surface area (ECSA) and facilitates assessing the key role of surface

  7. Progress in Aluminum Electrolysis Control and Future Direction for Smart Aluminum Electrolysis Plant

    NASA Astrophysics Data System (ADS)

    Zhang, Hongliang; Li, Tianshuang; Li, Jie; Yang, Shuai; Zou, Zhong

    2017-02-01

    The industrial aluminum reduction cell is an electrochemistry reactor that operates under high temperatures and highly corrosive conditions. However, these conditions have restricted the measurement of key control parameters, making the control of aluminum reduction cells a difficult problem in the industry. Because aluminum electrolysis control systems have a significant economic influence, substantial research has been conducted on control algorithms, control systems and information systems for aluminum reduction cells. This article first summarizes the development of control systems and then focuses on the progress made since 2000, including alumina concentration control, temperature control and electrolyte molecular ratio control, fault diagnosis, cell condition prediction and control system expansion. Based on these studies, the concept of a smart aluminum electrolysis plant is proposed. The frame construction, key problems and current progress are introduced. Finally, several future directions are discussed.

  8. Progress in Aluminum Electrolysis Control and Future Direction for Smart Aluminum Electrolysis Plant

    NASA Astrophysics Data System (ADS)

    Zhang, Hongliang; Li, Tianshuang; Li, Jie; Yang, Shuai; Zou, Zhong

    2016-10-01

    The industrial aluminum reduction cell is an electrochemistry reactor that operates under high temperatures and highly corrosive conditions. However, these conditions have restricted the measurement of key control parameters, making the control of aluminum reduction cells a difficult problem in the industry. Because aluminum electrolysis control systems have a significant economic influence, substantial research has been conducted on control algorithms, control systems and information systems for aluminum reduction cells. This article first summarizes the development of control systems and then focuses on the progress made since 2000, including alumina concentration control, temperature control and electrolyte molecular ratio control, fault diagnosis, cell condition prediction and control system expansion. Based on these studies, the concept of a smart aluminum electrolysis plant is proposed. The frame construction, key problems and current progress are introduced. Finally, several future directions are discussed.

  9. Direct ELISA.

    PubMed

    Lin, Alice V

    2015-01-01

    First described by Engvall and Perlmann, the enzyme-linked immunosorbent assay (ELISA) is a rapid and sensitive method for detection and quantitation of an antigen using an enzyme-labeled antibody. Besides routine laboratory usage, ELISA has been utilized in medical field and food industry as diagnostic and quality control tools. Traditionally performed in 96-well or 384-well polystyrene plates, the technology has expanded to other platforms with increase in automation. Depending on the antigen epitope and availability of specific antibody, there are variations in ELISA setup. The four basic formats are direct, indirect, sandwich, and competitive ELISAs. Direct ELISA is the simplest format requiring an antigen and an enzyme-conjugated antibody specific to the antigen. This chapter describes the individual steps for detection of a plate-bound antigen using a horseradish peroxidase (HRP)-conjugated antibody and luminol-based enhanced chemiluminescence (ECL) substrate. The methodological approach to optimize the assay by chessboard titration is also provided.

  10. DIRECTIONAL COUPLERS

    DOEpatents

    Nigg, D.J.

    1961-12-01

    A directional coupler of small size is designed. Stripline conductors of non-rectilinear configuration, and separated from each other by a thin dielectric spacer. cross each other at least at two locations at right angles, thus providing practically pure capacitive coupling which substantially eliminates undesirable inductive coupling. The conductors are sandwiched between a pair of ground planes. The coupling factor is dependent only on the thickness and dielectric constant of the dielectric spacer at the point of conductor crossover. (AEC)

  11. DIRECTIONAL ANTENNA

    DOEpatents

    Bittner, B.J.

    1958-05-20

    A high-frequency directional antenna of the 360 d scaring type is described. The antenna has for its desirable features the reduction in both size and complexity of the mechanism for rotating the antenna through its scanning movement. These advantages result from the rotation of only the driven element, the reflector remaining stationary. The particular antenna structure comprises a refiector formed by a plurality of metallic slats arranged in the configuration of an annular cage having the shape of a zone of revolution. The slats are parallel to each other and are disposed at an angle of 45 d to the axis of the cage. A directional radiator is disposed inside the cage at an angle of 45 d to the axis of the cage in the same direction as the reflecting slats which it faces. As the radiator is rotated, the electromagnetic wave is reflected from the slats facing the radiator and thereafter passes through the cage on the opposite side, since these slats are not parallel with the E vector of the wave.

  12. Controlling Water Intercalation Is Key to a Direct Graphene Transfer.

    PubMed

    Verguts, Ken; Schouteden, Koen; Wu, Cheng-Han; Peters, Lisanne; Vrancken, Nandi; Wu, Xiangyu; Li, Zhe; Erkens, Maksiem; Porret, Clement; Huyghebaert, Cedric; Van Haesendonck, Chris; De Gendt, Stefan; Brems, Steven

    2017-10-11

    The key steps of a transfer of two-dimensional (2D) materials are the delamination of the as-grown material from a growth substrate and the lamination of the 2D material on a target substrate. In state-of-the-art transfer experiments, these steps remain very challenging, and transfer variations often result in unreliable 2D material properties. Here, it is demonstrated that interfacial water can insert between graphene and its growth substrate despite the hydrophobic behavior of graphene. It is understood that interfacial water is essential for an electrochemistry-based graphene delamination from a Pt surface. Additionally, the lamination of graphene to a target wafer is hindered by intercalation effects, which can even result in graphene delamination from the target wafer. For circumvention of these issues, a direct, support-free graphene transfer process is demonstrated, which relies on the formation of interfacial water between graphene and its growth surface, while avoiding water intercalation between graphene and the target wafer by using hydrophobic silane layers on the target wafer. The proposed direct graphene transfer also avoids polymer contamination (no temporary support layer) and eliminates the need for etching of the catalyst metal. Therefore, recycling of the growth template becomes feasible. The proposed transfer process might even open the door for the suggested atomic-scale interlocking-toy-brick-based stacking of different 2D materials, which will enable a more reliable fabrication of van der Waals heterostructure-based devices and applications.

  13. A new cumulene diiron complex related to the active site of Fe-only hydrogenases and its phosphine substituted derivatives: synthesis, electrochemistry and structural characterization.

    PubMed

    Wen, Na; Xu, Fenfen; Feng, Yanan; Du, Shaowu

    2011-09-01

    A new cumulene diiron complex related to the Fe-only hydrogenase active site [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(6)] (1) was obtained by treatment of (μ-LiS)(2)Fe(2)(CO)(6) with excess 1,4-dichloro-2-butyne. By controllable CO displacement of 1 with PPh(3) and bis(diphenylphosphino)methane (dppm), mono- and di-substituted complexes, namely [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(5)L] (2: L=PPh(3); 3: L=dppm) and [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(4)L(2)] (4: L=PPh(3); 5: L=dppm) could be prepared in moderate yields. Treatment of 1 with bis(diphenylphosphino)ethane (dppe) afforded a double butterfly complex [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(5)](2)(μ-dppe) (7). With dppm in refluxing toluene, a dppm-bridged complex [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(4)(μ-dppm)] (6) was obtained. These model complexes were characterized by IR, (1)H, (31)P NMR spectra and the molecular structures of 1, 2 and 5-7 were determined by single crystal X-ray analyses. The electrochemistry of 1-3 was studied and the electrocatalytic property of 1 was investigated for proton reduction in the presence of HOAc. Copyright © 2011 Elsevier Inc. All rights reserved.

  14. Electrochemistry, surface plasmon resonance, and quartz crystal microbalance: an associative study on cytochrome c adsorption on pyridine tail-group monolayers on gold.

    PubMed

    Paulo, Tércio de F; de Sousa, Ticyano P; de Abreu, Dieric S; Felício, Nathalie H; Bernhardt, Paul V; Lopes, Luiz G de F; Sousa, Eduardo H S; Diógenes, Izaura C N

    2013-07-25

    Quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and electrochemistry techniques were used to study the electron-transfer (ET) reaction of cytochrome c (Cyt c) on gold surfaces modified with thionicotinamide, thioisonicotinamide, 4-mercaptopyridine, 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol, 5-phenyl-1,3,4-oxadiazole-2-thiol, 4,4'-bipyridine, and 4,4'-dithiopyridine. The electrochemical results showed that the ET process is complex, being chiefly diffusional with steps depending on the orientation of the pyridine or phenyl tail group of the modifiers. The correlation between the electrochemical results and those acquired by SPR and QCM indicated the presence of an adlayer of Cyt c adsorbed on the thiolate SAMs. This adlayer, although being not electroactive, is essential to assess the ET reaction of Cyt c in solution. The results presented in this work are consistent with the statement (Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Electroanal. Chem. 1995, 394, 149-154) that the ET reaction of Cyt c can be explained in terms of the through-bond tunneling mechanism.

  15. Synthetic Control of Crystallite Size of Silver Vanadium Phosphorous Oxide (Ag0.50VOPO4·1.9H2O): Impact on Electrochemistry

    DOE PAGES

    Huie, Matthew M.; Marschilok, Amy C.; Takeuchi, Esther S.; ...

    2017-04-12

    Here, this report describes a synthetic approach to control the crystallite size of silver vanadium phosphorous oxide, Ag0.50VOPO4·1.9H2O, and the impact on electrochemistry in lithium based batteries. Ag0.50VOPO4·1.9H2O was synthesized using a stirred hydrothermal method over a range of temperatures. X-ray diffraction (XRD) was used to confirm the crystalline phase and the crystallite size sizes of 11, 22, 38, 40, 49, and 120 nm. Particle shape was plate-like with edges <1 micron to >10 microns. Under galvanostatic reduction the samples with 22 nm crystallites and 880 nm particles produced the highest capacity, ~25% more capacity than the 120 nm sample.more » Notably, the 11 nm sample resulted in reduced delivered capacity and higher resistance consistent with increased grain boundaries contributing to resistance. Under intermittent pulsing ohmic resistance decreased with increasing crystallite size from 11 nm to 120 nm implying that electrical conduction within a crystal is more facile than between crystallites and across grain boundaries. Finally, this systematic study of material dimension shows that crystallite size impacts deliverable capacity as well as cell resistance where both interparticle and intraparticle transport are important.« less

  16. Investigation of the electrochemical oxidation products of zotepine and their fragmentation using on-line electrochemistry/electrospray ionization mass spectrometry.

    PubMed

    Nozaki, Kazuyoshi; Kitagawa, Hiroshi; Kimura, Sumihisa; Kagayama, Akira; Arakawa, Ryuichi

    2006-05-01

    When zotepine, an antipsychotic drug, was electrochemically oxidized using electrospray ionization mass spectrometry (ESI-MS) coupled with a microflow electrolytic cell, [M + 16 + H]+ (m/z 348), [M-H]+ (m/z 330) and [M-14 + H]+ (m/z 318) were observed as electrochemical oxidation product ions (M represents the zotepine molecule). Although a major fragment ion that was derived from the dimethyl aminoethyl moiety was observed only at m/z 72 in the collision-induced dissociation (CID) spectrum of zotepine, new fragments such as m/z 315 and 286 ions could be generated in the CID spectrum by combining electrochemical oxidation and CID. Since these fragments were relatively specific with high ion strength, it was thought that they would be useful for developing a sensitive LC-MS/MS assay. The S-oxide and N-demethylated products were detected by electrolysis assuring that a portion of P450 metabolites of zotepine could be mimicked by the electrochemistry/electrospray ionization mass spectrometry (EC/ESI-MS) system.

  17. The Microscale Synthesis and Electrochemistry of Low-Valent Mononuclear Complexes (h3-C3H5)Fe(CO)3 X (X = I, Br, Cl)

    NASA Astrophysics Data System (ADS)

    Mocellin, Enrico; Russell, Richard; Ravera, Mauro

    1998-06-01

    The experimental content of this paper will appeal to pedagogues and students who might be looking for new ideas that have an element of challenge. By combining experimental procedures which place microscale, chemical synthesis, and an inclusive, unified, product characterization in perspective, we have afforded the student the scope to obtain progressive, disciplined results and the opportunity to discuss these in the subsequent reporting. By this process, it is our experience that the students often identify with the practical work that is being undertaken, and they develop considerable empathy during their contribution to the "discovery" process that this laboratory program offers. The experimental work can be abbreviated to a single compound, subdivided into synthesis or electrochemistry, or extended to macroscale and other instrumental techniques of characterization, thus offering opportunities to accommodate time constraints, class results combination and discussion, and individual student enthusiasm. We believe that having to accept and/or constructively criticize sequential experimental results, collected by fellow students, mimics more realistically the practice of chemistry at the workplace and can build enthusiasm and elicit contagious fellowship from the class. All of these aspects can simply be achieved by utilizing the listed journals and references therein. Most importantly, it affords the students the opportunity to extricate themselves as innocent bystanders from the conventional "single experiment" practical laboratory to a path of practice and achievement in the scientific method.

  18. Forensic analyses of explosion debris from the January 2, 1992 Pd/D{sub 2}O electrochemistry incident at SRI International

    SciTech Connect

    Andresen, B.; Whipple, R.; Vandervoort, D.; Grant, P.

    1992-08-15

    The January 2, 1992 explosion in an electrochemistry laboratory at SRI International (SRI) resulted in the death of scientist Andrew Riley, and gained some notoriety due to its association with experimental work in the controversial field of cold fusion research. Selected components of explosion debris were subjected to forensic analyses at LLNL to elucidate potential causes of, or contributing factors to, the explosion. Interrogation of the debris by LLNL encompassed nuclear, chemical, physical, and materials investigations. Nuclear studies for the determination of tritium and neutron-activation products in stainless steel and brass were negative. No evidence of signature species indicative of orthodox nuclear events was detected. The inorganic and particulate analyses were likewise negative with respect to residues of unexpected chemical species. Such target compounds included conventional explosives, accelerants, propellants, or any exceptional industrial chemicals. The GC-MS analyses of trace organic components in the explosion debris provided perhaps the most interesting results obtained at LLNL. Although no evidence of organic explosives, oxidizers, or other unusual compounds was detected, the presence of a hydrocarbon oil in the interior of the electrochemical cell was established. It is likely that its source was lubricating fluid from the machining of the metal cell components. If residues of organic oils are present during electrolysis experiments, the potential exists for an explosive reaction in the increasingly enriched oxygen atmosphere within the headspace of a metal cell.

  19. Dispersion of nanocrystalline Fe3O4 within composite electrodes: Insights on battery-related electrochemistry

    SciTech Connect

    David C. Bock; Takeuchi, Kenneth J.; Pelliccione, Christopher J.; Zhang, Wei; Wang, Jiajun; Knehr, K. W.; Wang, Jun; Wang, Feng; West, Alan C.; Marschilok, Amy C.; Takeuchi, Esther S.

    2016-04-20

    Aggregation of nanosized materials in composite lithium-ion-battery electrodes can be a significant factor influencing electrochemical behavior. In this study, aggregation was controlled in magnetite, Fe3O4, composite electrodes via oleic acid capping and subsequent dispersion in a carbon black matrix. A heat treatment process was effective in the removal of the oleic acid capping agent while preserving a high degree of Fe3O4 dispersion. Electrochemical testing showed that Fe3O4 dispersion is initially beneficial in delivering a higher functional capacity, in agreement with continuum model simulations. However, increased capacity fade upon extended cycling was observed for the dispersed Fe3O4 composites relative to the aggregated Fe3O4 composites. X-ray absorption spectroscopy measurements of electrodes post cycling indicated that the dispersed Fe3O4 electrodes are more oxidized in the discharged state, consistent with reduced reversibility compared with the aggregated sample. Higher charge-transfer resistance for the dispersed sample after cycling suggests increased surface-film formation on the dispersed, high-surface-area nanocrystalline Fe3O4 compared to the aggregated materials. Furthermore, this study provides insight into the specific effects of aggregation on electrochemistry through a multiscale view of mechanisms for magnetite composite electrodes.

  20. One-step synthesis of large-scale graphene film doped with gold nanoparticles at liquid-air interface for electrochemistry and Raman detection applications.

    PubMed

    Zhang, Panpan; Huang, Ying; Lu, Xin; Zhang, Siyu; Li, Jingfeng; Wei, Gang; Su, Zhiqiang

    2014-07-29

    We demonstrated a facile one-step synthesis strategy for the preparation of a large-scale reduced graphene oxide multilayered film doped with gold nanoparticles (RGO/AuNP film) and applied this film as functional nanomaterials for electrochemistry and Raman detection applications. The related applications of the fabricated RGO/AuNP film in electrochemical nonenzymatic H2O2 biosensor, electrochemical oxygen reduction reaction (ORR), and surface-enhanced Raman scattering (SERS) detection were investigated. Electrochemical data indicate that the H2O2 biosensor fabricated by RGO/AuNP film shows a wide linear range, low limitation of detection, high selectivity, and long-term stability. In addition, it was proved that the created RGO/AuNP film also exhibits excellent ORR electrochemical catalysis performance. The created RGO/AuNP film, when serving as SERS biodetection platform, presents outstanding performances in detecting 4-aminothiophenol with an enhancement factor of approximately 5.6 × 10(5) as well as 2-thiouracil sensing with a low concentration to 1 μM. It is expected that this facile strategy for fabricating large-scale graphene film doped with metallic nanoparticles will spark inspirations in preparing functional nanomaterials and further extend their applications in drug delivery, wastewater purification, and bioenergy.