WorldWideScience

Sample records for direct electrochemistry etude

  1. Electrochemistry

    International Nuclear Information System (INIS)

    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. Electrochemistry

    International Nuclear Information System (INIS)

    Baek, Un Gi; Park, Su Mun

    2001-02-01

    This book starts introduction of electrochemistry, it describes reaction, cell, potentiometry glass electrode, Gouy-Chapman's theory, speed of electrode reaction, electrolyte solution with Debye-Huckel's theory, electrolyte conduction and diffusion, test way like coulometry and diffusion, test way like coulometry and rotated electrode, AC measurement and impedance, AC voltammetry, ellipsometry, electro analytical chemistry with anodic stripping voltametry and electrochemical sensors, electrochemistry material and reaction, electrochemistry and five appendixes.

  3. Direct electrochemistry of hemoglobin entrapped in dextran film on ...

    Indian Academy of Sciences (India)

    Direct electrochemistry of hemoglobin (Hb) entrapped in the dextran (De) film on the surface of a room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) modified carbon paste electrode (CILE) has been investigated. UV-Vis and FT-IR spectroscopy showed that Hb retained its native ...

  4. A Review on Direct Electrochemistry of Catalase for Electrochemical Sensors

    Directory of Open Access Journals (Sweden)

    Periasamy Arun Prakash

    2009-03-01

    Full Text Available 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 H2O2 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 H2O2 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 H2O2 determination. The benefits of immobilizing CAT in nanomaterial matrices have also been highlighted.

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

    Science.gov (United States)

    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.

  6. Direct electrochemistry of hemoglobin entrapped in dextran film on ...

    Indian Academy of Sciences (India)

    Administrator

    28. Li et al used single- walled carbon nanotube (SWCNT) and 1-hexyl-3- ... Electrochemistry of dextran/hemoglobin/carbon ionic liquid electrode. 273. 2.4 Procedures ..... used for the construction of H2O2 biosensor. Acknowledgement.

  7. Direct Electrochemistry of Horseradish Peroxidase-Gold Nanoparticles Conjugate

    Directory of Open Access Journals (Sweden)

    Chanchal K. Mitra

    2009-02-01

    Full Text Available We have studied the direct electrochemistry of horseradish peroxidase (HRP coupled to gold nanoparticles (AuNP using electrochemical techniques, which provide some insight in the application of biosensors as tools for diagnostics because HRP is widely used in clinical diagnostics kits. AuNP capped with (i glutathione and (ii lipoic acid was covalently linked to HRP. The immobilized HRP/AuNP conjugate showed characteristic redox peaks at a gold electrode. It displayed good electrocatalytic response to the reduction of H2O2, with good sensitivity and without any electron mediator. The covalent linking of HRP and AuNP did not affect the activity of the enzyme significantly. The response of the electrode towards the different concentrations of H2O2 showed the characteristics of Michaelis Menten enzyme kinetics with an optimum pH between 7.0 to 8.0. The preparation of the sensor involves single layer of enzyme, which can be carried out efficiently and is also highly reproducible when compared to other systems involving the layer-by-layer assembly, adsorption or encapsulation of the enzyme. The immobilized AuNP-HRP can be used for immunosensor applications

  8. Direct electrochemistry of nitrate reductase from the fungus Neurospora crassa.

    Science.gov (United States)

    Kalimuthu, Palraj; Ringel, Phillip; Kruse, Tobias; Bernhardt, Paul V

    2016-09-01

    We report the first direct (unmediated) catalytic electrochemistry of a eukaryotic nitrate reductase (NR). NR from the filamentous fungus Neurospora crassa, is a member of the mononuclear molybdenum enzyme family and contains a Mo, heme and FAD cofactor which are involved in electron transfer from NAD(P)H to the (Mo) active site where reduction of nitrate to nitrite takes place. NR was adsorbed on an edge plane pyrolytic graphite (EPG) working electrode. Non-turnover redox responses were observed in the absence of nitrate from holo NR and three variants lacking the FAD, heme or Mo cofactor. The FAD response is due to dissociated cofactor in all cases. In the presence of nitrate, NR shows a pronounced cathodic catalytic wave with an apparent Michaelis constant (KM) of 39μM (pH7). The catalytic cathodic current increases with temperature from 5 to 35°C and an activation enthalpy of 26kJmol(-1) was determined. In spite of dissociation of the FAD cofactor, catalytically activity is maintained. Copyright © 2016. Published by Elsevier B.V.

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

    Science.gov (United States)

    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.

  10. Fabrication of graphene–platinum nanocomposite for the direct electrochemistry and electrocatalysis of myoglobin

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Wei, E-mail: swyy26@hotmail.com [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 (China); College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Li, Linfang [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Lei, Bingxin [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 (China); Li, Tongtong; Ju, Xiaomei; Wang, Xiuzheng; Li, Guangjiu [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Sun, Zhenfan [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 (China)

    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. - Highlights: ► The GR–Pt nanocomposite was synthesized and employed for the fabrication of electrochemical biosensor. ► Direct electrochemistry of Mb in the nanocomposite was realized. ► The prepared biosensor exhibited excellent electrochemical response to the reduction of TCA.

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

    Science.gov (United States)

    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.

  12. Direct electrochemistry and electrocatalysis of glucose oxidase on three-dimensional interpenetrating, porous graphene modified electrode

    International Nuclear Information System (INIS)

    Cui, Min; Xu, Bing; Hu, Chuangang; Shao, Hui Bo; Qu, Liangti

    2013-01-01

    Direct electrochemistry of glucose oxidase (GOD) on three-dimensional (3D) interpenetrating porous graphene electrodes has been reported, which have been fabricated by one-step electrochemical reduction of graphene oxide (GO) from its aqueous suspension. The electrochemically reduced GO (ERGO) modified electrodes exhibited excellent electron transfer properties for GOD and enhanced the enzyme activity and stability by the assistance of chitosan. The immobilized GOD shows a fast electron transfer with the rate constant (k s ) of 6.05 s −1 . It is worth mentioning that in the air-saturated phosphate buffer solution without any mediator, the resultant modified electrodes exhibited low detection limit of 1.7 μM with wide linear range of 0.02–3.2 mM and high sensitivity and high selectivity for measuring glucose. It would also be extended to various enzymes and bioactive molecules to develop the biosensor or other bio-electrochemical devices

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

    Science.gov (United States)

    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.

  14. Direct electrochemistry of hemoglobin immobilized in CuO nanowire bundles.

    Science.gov (United States)

    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. Direct electrochemistry of glucose oxidase assembled on graphene and application to glucose detection

    International Nuclear Information System (INIS)

    Wu Ping; Shao Qian; Hu Yaojuan; Jin Juan; Yin Yajing; Zhang Hui; Cai Chenxin

    2010-01-01

    The direct electrochemistry of glucose oxidase (GOx) integrated with graphene was investigated. The voltammetric results indicated that GOx assembled on graphene retained its native structure and bioactivity, exhibited a surface-confined process, and underwent effective direct electron transfer (DET) reaction with an apparent rate constant (k s ) of 2.68 s -1 . This work also developed a novel approach for glucose detection based on the electrocatalytic reduction of oxygen at the GOx-graphene/GC electrode. The assembled GOx could electrocatalyze the reduction of dissolved oxygen. Upon the addition of glucose, the reduction current decreased, which could be used for glucose detection with a high sensitivity (ca. 110 ± 3 μA mM -1 cm -2 ), a wide linear range (0.1-10 mM), and a low detection limit (10 ± 2 μM). The developed approach can efficiently exclude the interference of commonly coexisting electroactive species due to the use of a low detection potential (-470 mV, versus SCE). Therefore, this study has not only successfully achieved DET reaction of GOx assembled on graphene, but also established a novel approach for glucose detection and provided a general route for fabricating graphene-based biosensing platform via assembling enzymes/proteins on graphene surface.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

    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 (k s ) of 2.83 s -1 . A much higher enzyme loading (1.12 x 10 -9 mol/cm 2 ) 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 (micro)A 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.

  17. Direct Electrochemistry of Horseradish Peroxidase on NiO Nanoflower Modified Electrode and Its Electrocatalytic Activity

    Directory of Open Access Journals (Sweden)

    Lijun Yan

    2016-09-01

    Full Text Available In this paper nickel oxide (NiO nanoflower was synthesized and used for the realization of direct electrochemistry of horseradish peroxidase (HRP. By using carbon ionic liquid electrode (CILE as the substrate electrode, NiO-HRP composite was casted on the surface of CILE with chitosan (CTS as the film forming material and the modified electrode was denoted as CTS/NiO-HRP/CILE. UV-Vis absorption and FT-IR spectra confirmed that HRP retained its native structure after mixed with NiO nanoflower. Direct electron transfer of HRP on the modified electrode was investigated by cyclic voltammetry with a pair of quasi-reversible redox waves appeared, indicating that the presence of NiO nanoflower on the electrode surface could accelerate the electron transfer rate between the electroactive center of HRP and the substrate electrode. Electrochemical behaviors of HRP on the modified electrode were carefully investigated. The HRP modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid with wider linear range and lower detection limit. Therefore the presence of NiO nanoflower could provide a friendly biocompatible interface for immobilizing biomolecules and keeping their native structure. The fabricated electrochemical biosensor displayed the advantages such as high sensitivity, good reproducibility and long-term stability. This work is licensed under a Creative Commons Attribution 4.0 International License.

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

    Directory of Open Access Journals (Sweden)

    Guang-Chao Zhao

    2013-06-01

    Full Text Available 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.

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

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

    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). - Graphical abstract: Direct electrochemistry of myoglobin was realized on a three-dimensional reduced graphene oxide and gold nanocomposite modified carbon ionic liquid electrode. - Highlights: • A three-dimensional reduced graphene oxide and gold composite was synthesized by electrodeposition. • Myoglobin was immobilized on the modified electrode to obtain an electrochemical sensor. • Direct electrochemistry of myoglobin was realized on the modified electrode. • The myoglobin modified electrode showed excellent electrocatalytic reduction to trichloroacetic acid.

  1. Direct electrochemistry of glucose oxidase and glucose biosensing on a hydroxyl fullerenes modified glassy carbon electrode.

    Science.gov (United States)

    Gao, Yun-Fei; Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, Bao-Lin; Hong, Jun; Sheibani, Nader; Ghourchian, Hedayatollah; Hong, Tao; Moosavi-Movahedi, Ali Akbar

    2014-10-15

    Direct electrochemistry of glucose oxidase (GOD) was achieved when GOD-hydroxyl fullerenes (HFs) nano-complex was immobilized on a glassy carbon (GC) electrode and protected with a chitosan (Chit) membrane. The ultraviolet-visible absorption spectrometry (UV-vis), transmission electron microscopy (TEM), and circular dichroism spectropolarimeter (CD) methods were utilized for additional characterization of the GOD, GOD-HFs and Chit/GOD-HFs. Chit/HFs may preserve the secondary structure and catalytic properties of GOD. The cyclic voltammograms (CVs) of the modified GC electrode showed a pair of well-defined quasi-reversible redox peaks with the formal potential (E°') of 353 ± 2 mV versus Ag/AgCl at a scan rate of 0.05 V/s. The heterogeneous electron transfer constant (ks) was calculated to be 2.7 ± 0.2s(-1). The modified electrode response to glucose was linear in the concentrations ranging from 0.05 to 1.0mM, with a detection limit of 5 ± 1 μM. The apparent Michaelis-Menten constant (Km(app)) was 694 ± 8 μM. Thus, the modified electrode could be applied as a third generation biosensor for glucose with high sensitivity, selectivity and low detection limit. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Ruping; Deng, Minqiang; Cui, Sanguan; Chen, Hong [Department of Chemistry and Institute for Advanced Study, Nanchang University, Nanchang 330031 (China); Qiu, Jianding, E-mail: jdqiu@ncu.edu.cn [Department of Chemistry and Institute for Advanced Study, Nanchang University, Nanchang 330031 (China)

    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.

  3. Immobilization, direct electrochemistry and electrocatalysis of hemoglobin on colloidal silver nanoparticles-chitosan film

    Energy Technology Data Exchange (ETDEWEB)

    Yu Chunmei [College of Chemistry and Chemical Engineering and Materials Science, Suzhou University, Suzhou 215123 (China); Institute of Analytical Chemistry for Life Science, School of Public Health, Nantong University, Nantong 226007 (China); Zhou Xiaohui [Institute of Analytical Chemistry for Life Science, School of Public Health, Nantong University, Nantong 226007 (China); Gu Haiying, E-mail: hygu@ntu.edu.c [Institute of Analytical Chemistry for Life Science, School of Public Health, Nantong University, Nantong 226007 (China)

    2010-12-01

    This paper reports on the fabrication and characterization of hemoglobin (Hb)-colloidal silver nanoparticles (CSNs)-chitosan film on the glassy carbon electrode and its application on electrochemical biosensing. CSNs could greatly enhance the electron transfer reactivity of Hb as a bridge. In the phosphate buffer solution with pH value of 7.0, Hb showed a pair of well-defined redox peaks with the formal potential (E{sup 0'}) of -0.325 V (vs. SCE). The immobilized Hb in the film maintained its biological activity, showing a surface-controlled process with the heterogeneous electron transfer rate constant (k{sub s}) of 1.83 s{sup -1} and displayed the same features of a peroxidase in the electrocatalytic reduction of oxygen and hydrogen peroxide (H{sub 2}O{sub 2}). The linear range for the determination of H{sub 2}O{sub 2} was from 0.75 {mu}M to 0.216 mM with a detection limit of 0.5 {mu}M (S/N = 3). Such a simple assemble method could offer a promising platform for further study on the direct electrochemistry of other redox proteins and the development of the third-generation electrochemical biosensors.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mascagni, Daniela Branco Tavares [São Paulo State University - UNESP, Sorocaba, São Paulo (Brazil); Miyazaki, Celina Massumi [Federal University of São Carlos, UFSCar, Campus Sorocaba, SP (Brazil); Cruz, Nilson Cristino da [São Paulo State University - UNESP, Sorocaba, São Paulo (Brazil); Leite de Moraes, Marli [Federal University of São Paulo, Unifesp, Campus São José dos Campos, SP (Brazil); Riul, Antonio [University of Campinas - Unicamp, Campinas, São Paulo (Brazil); Ferreira, Marystela, E-mail: marystela@ufscar.br [Federal University of São Carlos, UFSCar, Campus Sorocaba, SP (Brazil)

    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 13.4 μmol·L{sup ‐1} and sensitivity of 2.47 μA·cm{sup −2}·mmol{sup −1}·L for glucose with the (GPDDA/GPSS){sub 1}/(GPDDA/GOx){sub 2} architecture, whose thickness was 19.80 ± 0.28 nm, 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. - Highlights: • Direct electrochemistry of glucose oxidase at functionalized reduced graphene oxide. • Thickness (layer-by-layer) LbL film determined by Surface Plasmon Resonance (SPR). • Selective determination of glucose in the presence of several interferents. • Real sample test: commercial oral electrolyte solution and lactose-free milk.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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 13.4 μmol·L ‐1 and sensitivity of 2.47 μA·cm −2 ·mmol −1 ·L for glucose with the (GPDDA/GPSS) 1 /(GPDDA/GOx) 2 architecture, whose thickness was 19.80 ± 0.28 nm, 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. - Highlights: • Direct electrochemistry of glucose oxidase at functionalized reduced graphene oxide. • Thickness (layer-by-layer) LbL film determined by Surface Plasmon Resonance (SPR). • Selective determination of glucose in the presence of several interferents. • Real sample test: commercial oral electrolyte solution and lactose-free milk.

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

    Science.gov (United States)

    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.

  8. Bipolar electrochemistry.

    Science.gov (United States)

    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.

  9. Immobilization of horseradish peroxidase on self-assembled (3-mercaptopropyl)trimethoxysilane film: Characterization, direct electrochemistry, redox thermodynamics and biosensing

    International Nuclear Information System (INIS)

    Wu Fanghua; Hu Zhichao; Xu Jingjing; Tian Yuan; Wang Liwei; Xian Yuezhong; Jin Litong

    2008-01-01

    Highly organized (3-mercaptopropyl)trimethoxysilane (3-MPT) films have been prepared via self-assembled coupled with sol-gel linking technology. Horseradish peroxidase (HRP) is successfully immobilized onto the densely packed three-dimensional (3D) 3-MPT network and the direct electrochemistry of HRP is achieved without any electron mediators or promoters. Redox thermodynamics of HRP on the 3-MPT films, which is obtained from the temperature dependence of the reduction potential, suggests that the positive shift of redox potentials of HRP at the interface of 3-MPT originates from the solvent reorganization effects and conformational change of the polypeptide chain of HRP. Based on the direct electrochemistry and electrocatalytic ability of HRP, a sensitive third-generation amperometric H 2 O 2 biosensor is developed with two linear dependence ranges of 5.0 x 10 -7 to 1.0 x 10 -4 and 1.0 x 10 -4 to 2.0 x 10 -2 mol L -1

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

    Science.gov (United States)

    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. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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.

  12. Electrochemistry And Application Of Electrochemistry

    International Nuclear Information System (INIS)

    Jang, Hyang Dong

    1990-02-01

    This book introduces electrochemistry and applications of electrochemistry, SI unit system, solution, distribution ratios, concentration indicate, electrolyte and electrolytic dissociation, conduction of electrolyte dissolution, electrode potential such as gas electrode, Oxidation-reduction electrode and reversible cell, potential measurement by potentiometer law, acid-base like Bronsted-Lowry's acid-base and Lewis's acid-base, neutralization reaction and hydrolysis, zwitter ion, potentiometry, practical cell, polarization and electrolyte, electrolysis and electrical installation.

  13. Understanding the mechanism of direct electrochemistry of mitochondria-modified electrodes from yeast, potato and bovine sources at carbon paper electrodes

    International Nuclear Information System (INIS)

    Giroud, Fabien; Nicolo, Tera A.; Koepke, Sara J.; Minteer, Shelley D.

    2013-01-01

    Although mitochondria have been used for bio-electrochemistry for over 5 years, little is known about their direct electrochemistry mechanism. This paper focuses on developing a better understanding of the electron transfer mechanism of mitochondria from three different organisms at carbon electrodes. Yeast, potato and bovine mitochondria have been successfully isolated and immobilized onto Toray paper electrodes via vapor deposited silica. Organelle-modified electrodes were first characterized using cyclic voltammetry. Similar electrochemical signals were obtained for all organisms. Direct electron transfer was observed when a metabolite of the Krebs cycle was present in the buffer solution. Control experiments based on the immobilization of two electron carriers contained in mitochondria, cytochrome c and a quinone (coenzyme Q 10 ), tend to show the electron transfer mechanism to the carbon material comes from the quinone pool of the organelles. As quinones are known to be pH-dependent, we further investigated the response of the electrochemical signal of the three isolated mitochondria and the two electron carriers separately. The half wave potentials obtained from the organelles appeared to be pH-dependent and their variations are comparable to coenzyme Q 10 rather than cytochrome c. Finally, extraction of both the cytochrome c and the quinone pool from intact mitochondria was performed to validate our hypothesis that direct electrochemistry of mitochondria happens via the quinone pool. Electrochemistry of immobilized quinone-depleted mitochondria validated the hypothesis that the mitochondria are communicating with the electrodes through the quinone pool

  14. Direct electrochemistry and electrocatalysis of glucose oxidase immobilized on reduced graphene oxide and silver nanoparticles nanocomposite modified electrode.

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

    Shamsipur, Mojtaba; Amouzadeh Tabrizi, Mahmoud

    2014-01-01

    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 (pH 7.0) 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. - Highlights: • A direct electron transfer reaction of glucose oxidase was observed on GCE/ERGO/SDS. • This composite film was successfully applied in preparation of glucose biosensor. • The detection limit of the biosensor was estimated to be 40.8 μM. • The results from the sensor were similar to those obtained from the clinical analyzer

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

    Energy Technology Data Exchange (ETDEWEB)

    Shamsipur, Mojtaba; Amouzadeh Tabrizi, Mahmoud, E-mail: mahmoud.tabrizi@gmail.com

    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 (pH 7.0) with a scan rate of 50 mV/s. The average surface coverage is 2.62 × 10{sup −10} mol cm{sup −2}. The resulting biosensor exhibited a good response to glucose with linear range from 1 to 8 mM (R{sup 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. - Highlights: • A direct electron transfer reaction of glucose oxidase was observed on GCE/ERGO/SDS. • This composite film was successfully applied in preparation of glucose biosensor. • The detection limit of the biosensor was estimated to be 40.8 μM. • The results from the sensor were similar to those obtained from the clinical analyzer.

  17. Potassium-doped carbon nanotubes toward the direct electrochemistry of cholesterol oxidase and its application in highly sensitive cholesterol biosensor

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaorong [State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Xu Jingjuan, E-mail: xujj@nju.edu.cn [State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Chen Hongyuan [State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China)

    2011-10-30

    We demonstrate herein a newly developed serum total cholesterol biosensor by using the direct electron transfer of cholesterol oxidase (ChOx), which is based on the immobilization of cholesterol oxidase and cholesterol esterase (ChEt) on potassium-doped multi-walled carbon nanotubes (KMWNTs) modified electrodes. The KMWNTs accelerate the electron transfer from electrode surface to the immobilized ChOx, achieving the direct electrochemistry of ChOx and maintaining its bioactivity. As a new platform in cholesterol analysis, the resulting electrode (ChOx/KMWNTs/GCE) exhibits a sensitive response to free cholesterol, with a linear range of 0.050-16.0 {mu}mol L{sup -1} and a detection limit of 5.0 nmol L{sup -1} (S/N = 3). Coimmobilization of ChEt and ChOx (ChEt/ChOx/KMWNTs/GCE) allows the determination of both free cholesterol and esterified cholesterol. The resulting biosensor shows the same linear range of 0.050-16.0 {mu}mol L{sup -1} for free cholesterol and cholesteryl oleate, with the detection limit of 10.0 and 12.0 nmol L{sup -1} (S/N = 3), respectively. The concentrations of total (free and esterified) cholesterol in human serum samples, determined by using the techniques developed in the present study, are in good agreement with those determined by the well-established techniques using the spectrophotometry.

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

    Science.gov (United States)

    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.

  19. Novel urchin-like In2O3–chitosan modified electrode for direct electrochemistry of glucose oxidase and biosensing

    International Nuclear Information System (INIS)

    Yang Zhanjun; Huang Xiaochun; Zhang Rongcai; Li Juan; Xu Qin; Hu Xiaoya

    2012-01-01

    Highlights: ► The urchin-like In 2 O 3 –CS film is proposed for the immobilization of protein. ► The direct electrochemistry of glucose oxidase and biosensing was studied. ► The constructed glucose biosensor shows excellent performances. ► This matrix provides a new and efficient approach for the direct electrochemistry. - Abstract: A novel urchin-like In 2 O 3 –chitosan modified glassy carbon electrode (GCE) is for the first time prepared. The direct electrochemistry of glucose oxidase (GOD) immobilized on the surface of modified GCE and biosensing are studied. The urchin-like In 2 O 3 nanostructure-based matrix has large specific surface area and provides a favorable and biocompatible microenvironment for promoting the direct electron transfer between proteins and electrode surface. The properties of different modified electrode are characterized by scanning electron microscopy (SEM), electrochemical impedance spectra (EIS), UV–vis spectroscopy, Fourier transform infrared spectroscopy (FTIR) and cyclic voltammetry, respectively. The constructed glucose biosensor shows wide linear range (5.0 × 10 −6 to 1.3 × 10 −3 M), low detection limit (1.9 × 10 −6 M), a Michaelis–Menten constant of 0.37 mM. The proposed biosensor has good sensitivity, excellent selectivity, good reproducibility and stability. This urchin-like In 2 O 3 –chitosan matrix provides a new approach and efficient matrix for the direct electrochemistry of proteins and developing novel types of biosensors.

  20. In situ STM imaging and direct electrochemistry of Pyrococcus furiosus ferredoxin assembled on thiolate-modified Au(111) surfaces

    DEFF Research Database (Denmark)

    Zhang, Jingdong; Christensen, Hans Erik Mølager; Ooi, Bee Lean

    2004-01-01

    We have addressed here electron transfer (ET) of Pyrococcus furiosus ferredoxin (PfFd, 7.5 kDa) in both homogeneous solution using edge plane graphite (EPG) electrodes and in the adsorbed state by electrochemistry on surface-modified single-crystal Au(111) electrodes, This has been supported...... by surface microscopic structures of PfFd monolayers, as revealed by scanning tunneling microscopy under potential control (in situ STM). Direct ET between PfFd in phosphate buffer solution, pH 7.9, and EPG electrodes is observed in the presence of promoters. Neomycin gives rise to a pair of redox peaks...... with a formal potential of ca -430 mV (vs SCE), corresponding to [3Fe-4S](1+/0). The presence of an additional promoter, which can be propionic acid, alanine, or cysteine, induces a second pair of redox peaks at similar to-900 mV (vs SCE) arising from [3Fe-4S](0/1-). A robust neomycin-PfFd complex was detected...

  1. Analytical and physical electrochemistry

    CERN Document Server

    Girault, Hubert H

    2004-01-01

    The study of electrochemistry is pertinent to a wide variety of fields, including bioenergetics, environmental sciences, and engineering sciences. In addition, electrochemistry plays a fundamental role in specific applications as diverse as the conversion and storage of energy and the sequencing of DNA.Intended both as a basic course for undergraduate students and as a reference work for graduates and researchers, Analytical and Physical Electrochemistry covers two fundamental aspects of electrochemistry: electrochemistry in solution and interfacial electrochemistry. By bringing these two subj

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

    International Nuclear Information System (INIS)

    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 (Fe 3 O 4 ). The large surface area of Fe 3 O 4 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 Fe 3 O 4 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 Fe 3 O 4 nanoparticles were studied by the zeta potential measurement. Electrochemical impedance spectroscopy (EIS) of the SC/F/HRP/GCE electrode displays Fe 3 O 4 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 H 2 O 2 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. (paper)

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

    Science.gov (United States)

    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.

  4. Direct electrochemistry and electrocatalysis of horseradish peroxidase based on halloysite nanotubes/chitosan nanocomposite film

    Energy Technology Data Exchange (ETDEWEB)

    Sun Xiumei; Zhang Yao; Shen Hebai [Department of Chemistry, College of Life and Environmental Sciences, Shanghai Normal University, 100 Guilin Road, Shanghai 200234 (China); Jia Nengqin, E-mail: nqjia@shnu.edu.c [Department of Chemistry, College of Life and Environmental Sciences, Shanghai Normal University, 100 Guilin Road, Shanghai 200234 (China)

    2010-12-30

    The novel halloysite nanotubes/chitosan (HNTs/Chi) composite films were firstly explored to utilize for the immobilization of horseradish peroxidase (HRP) and their bioelectrochemical properties were studied, in which the biopolymer chitosan was used as a binder to increase film adherence on glassy carbon (GC) electrode. UV-vis and FTIR spectroscopy demonstrated that HRP in the composite film could retain its native secondary structure. A pair of well-defined redox peaks of HRP was obtained at the HRP/HNTs/Chi composite film-modified electrode, exhibiting its fast direct electron transfer (DET). Furthermore, the immobilized HRP displayed its good electrocatalytic activity for the reduction of hydrogen peroxide (H{sub 2}O{sub 2}). The results demonstrate that the HNTs/Chi composite film may improve the enzyme loading with the retention of bioactivity and greatly promote the direct electron transfer, which can be attributed to its unique tubular structure, high specific surface area, and good biocompatibility.

  5. Modern electrochemistry and industry

    International Nuclear Information System (INIS)

    Kim, Sun Yong

    1985-04-01

    This book is divided into fifteen chapters on modern electrochemistry and industry. The contents of this book are electrochemistry and industry, electrochemistry for electrolyte like ionic mobility quantity of activity of electrolyte, potential balance system like cell potential, concentration cell and membrane potential, electrochemical kinetics, electrochemistry for surfactant, electrochemistry for electrolysis test such as polarography, chronopotentiometry and Cyclic voltametry, electrolysis reactor NaOH electrolysis industry, H 2 O electrolysis, molten metal electrolysis, copper electrolysis, battery and electro-organic chemistry.

  6. Amperometric biosensor based on direct electrochemistry of hemoglobin in poly-allylamine (PAA) film

    International Nuclear Information System (INIS)

    Kafi, A.K.M.; Lee, Dong-Yun; Park, Sang-Hyun; Kwon, Young-Soo

    2007-01-01

    Hemoglobin (Hb) was immobilized in poly-allylamine (PAA) film onto the gold electrode by layer by layer (LBL) method. The modified electrode exhibited a pair of well-defined peaks during cyclic voltammetry, which was attributed from the direct electron transfer of heme proteins. The immobilized Hb showed an excellent electrocatalytical response to the reduction of hydrogen peroxide. The sensor exhibited a fast response and high sensitivity. Through the use of optimized conditions, the linear range for H 2 O 2 detection was from 2.5 x 10 -6 M to 5 x 10 -4 M with detection limit of 0.2 μM. The proposed biosensor showed long-lasting stability and excellent reproducibility

  7. Direct electrochemistry and electrocatalysis of hemoglobin protein entrapped in graphene and chitosan composite film.

    Science.gov (United States)

    Xu, Huifeng; Dai, Hong; Chen, Guonan

    2010-04-15

    A novel, biocompatible sensing strategy based on graphene and chitosan composite film for immobilizing the hemoglobin protein was firstly adopted. The direct electron transfer and bioelectrocatalytic activity of hemoglobin after incorporation into the composite film were investigated. A pair of reversible redox waves of hemoglobin was appeared, and hemoglobin could exhibit its bioelectrocatalytic activity toward H(2)O(2) in a long term. Such results indicated that graphene and chitosan composite could be a friendly biocompatible interface for immobilizing biomolecules and keeping their native structure. Furthermore, the appearance of graphene in the composite film could facilitate the electron transfer between matrix and the electroactive center of hemoglobin. Hence, this graphene and chitosan based protocol would be a promising platform for protein immobilization and biosensor preparation. (c) 2010 Elsevier B.V. All rights reserved.

  8. Direct electrochemistry of horseradish peroxidase immobilized on electrografted 4-ethynylphenyl film via click chemistry

    International Nuclear Information System (INIS)

    Ran Qin; Peng Ru; Liang Cong; Ye Siqiu; Xian Yuezhong; Zhang Wenjing; Jin Litong

    2011-01-01

    Graphical abstract: Hydrogen peroxide biosensor was developed based on electrochemically assisted aryldiazonium salt chemistry and click chemistry. Highlights: → A simple, versatile two-step approach, which is based on electrochemically assisted aryldiazonium salt chemistry and Cu(I)-catalyzed azide alkyne cycloaddition (CuAAC) reaction has been developed for covalent redox proteins immobilization and biosensing for the first time. In this work, azido group modified HRP was covalently grafted on 4-ethylnylphenyl diazonium compound via CuAAC reaction and a novel electrochemical hydrogen peroxide biosensor was successfully fabricated. - Abstract: In this paper, a simple two-step approach for redox protein immobilization was introduced. Firstly, alkynyl-terminated film was formed on electrode surface by electrochemical reduction of 4-ethylnylphenyl (4-EP) diazonium compound. Then, horseradish peroxidase (HRP) modified with azido group was covalently immobilized onto the electrografted film via click reaction. Reflection absorption infrared (RAIR) spectroscopy and electrochemical methods were used to characterize the modification process. The results indicate that HRP retains its native structure and shows fast direct electron transfer. Moreover, the immobilized HRP shows excellent electrocatalytic reduction activity toward H 2 O 2 with a linear range of 5.0 x 10 -6 to 9.3 x 10 -4 mol L -1 .

  9. Direct electrochemistry of horseradish peroxidase immobilized on electrografted 4-ethynylphenyl film via click chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Ran Qin; Peng Ru; Liang Cong; Ye Siqiu [Department of Chemistry, East China Normal University, Shanghai 200062 (China); Xian Yuezhong, E-mail: yzxian@chem.ecnu.edu.cn [Department of Chemistry, East China Normal University, Shanghai 200062 (China); Zhang Wenjing; Jin Litong [Department of Chemistry, East China Normal University, Shanghai 200062 (China)

    2011-07-04

    Graphical abstract: Hydrogen peroxide biosensor was developed based on electrochemically assisted aryldiazonium salt chemistry and click chemistry. Highlights: > A simple, versatile two-step approach, which is based on electrochemically assisted aryldiazonium salt chemistry and Cu(I)-catalyzed azide alkyne cycloaddition (CuAAC) reaction has been developed for covalent redox proteins immobilization and biosensing for the first time. In this work, azido group modified HRP was covalently grafted on 4-ethylnylphenyl diazonium compound via CuAAC reaction and a novel electrochemical hydrogen peroxide biosensor was successfully fabricated. - Abstract: In this paper, a simple two-step approach for redox protein immobilization was introduced. Firstly, alkynyl-terminated film was formed on electrode surface by electrochemical reduction of 4-ethylnylphenyl (4-EP) diazonium compound. Then, horseradish peroxidase (HRP) modified with azido group was covalently immobilized onto the electrografted film via click reaction. Reflection absorption infrared (RAIR) spectroscopy and electrochemical methods were used to characterize the modification process. The results indicate that HRP retains its native structure and shows fast direct electron transfer. Moreover, the immobilized HRP shows excellent electrocatalytic reduction activity toward H{sub 2}O{sub 2} with a linear range of 5.0 x 10{sup -6} to 9.3 x 10{sup -4} mol L{sup -1}.

  10. Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in graphene oxide–Nafion nanocomposite film

    International Nuclear Information System (INIS)

    Zhang Lili; Cheng Huhu; Zhang Huimin; Qu Liangti

    2012-01-01

    Direct electron transfer of horseradish peroxidase (HRP) immobilized in graphene oxide (GO)–Nafion nanocomposite film and its application as a new biosensor was investigated with electrochemical methods. Immobilized HRP shows a pair of well-defined redox waves and retains its bioelectrocatalytic activity for the reduction of H 2 O 2 and O 2 . As a new sensor with excellent electrocatalytic response to the reduction of H 2 O 2 and O 2 , calibrations with good linear relationships were obtained from 1.0 μmol L −1 to 1.0 mmol L −1 for H 2 O 2 and from 0.5 μmol L −1 to 18.6 μmol L −1 for O 2 with the detection limits of 4.0 × 10 −7 mol L −1 for H 2 O 2 and 1.0 × 10 −7 mol L −1 for O 2 at a signal-to-noise ratio of 3. Additionally, the responses showed Michaelis–Menten behavior with K m app values of 0.684 mmol L −1 for H 2 O 2 and 0.0160 mmol L −1 for O 2 . Moreover, the cathodic peak current of an HRP/GO/Nafion/GCE biosensor decreases by less than 5% after 4 weeks. These results reveal that GO can be conveniently incorporated into a polymer nanocomposite for fabrication of new GO-based biosensors.

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

    Science.gov (United States)

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Direct electrochemistry of blue copper proteins at boron-doped diamond electrodes

    Energy Technology Data Exchange (ETDEWEB)

    McEvoy, James P. [Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA (United Kingdom); Foord, John S. [Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA (United Kingdom)]. E-mail: john.foord@chem.ox.ac.uk

    2005-05-05

    Boron-doped diamond (BDD) is a promising electrode material for use in the spectro-electrochemical study of redox proteins and, in this investigation, cyclic voltammetry was used to obtain quasi-reversible electrochemical responses from two blue copper proteins, parsley plastocyanin and azurin from Pseudomonas aeruginosa. No voltammetry was observed at the virgin electrodes, but signals were observed if the electrodes were anodised, or abraded with alumina, prior to use. Plastocyanin, which has a considerable overall negative charge and a surface acidic patch which is important in forming a productive electron transfer complex with its redox partners, gave a faradaic signal at pre-treated BDD only in the presence of neomycin, a positively charged polyamine. The voltammetry of azurin, which has a small overall charge and no surface acidic patch, was obtained identically in the presence and absence of neomycin. Investigations were also carried out into the voltammetry of two site-directed mutants of azurin, M64E azurin and M44K azurin, each of which introduce a charge into the protein's surface hydrophobic patch. The oxidizing and cleaning effects of the BDD electrode pre-treatments were studied electrochemically using two inorganic probe ions, Fe(China){sub 6} {sup 3-} and Ru(NH{sub 3}){sub 6} {sup 3+}, and by X-ray photoelectron spectroscopy (XPS). All of the electrochemical results are discussed in relation to the electrostatic and hydrophobic contributions to the protein/diamond electrochemical interaction.

  13. Direct electrochemistry of blue copper proteins at boron-doped diamond electrodes

    International Nuclear Information System (INIS)

    McEvoy, James P.; Foord, John S.

    2005-01-01

    Boron-doped diamond (BDD) is a promising electrode material for use in the spectro-electrochemical study of redox proteins and, in this investigation, cyclic voltammetry was used to obtain quasi-reversible electrochemical responses from two blue copper proteins, parsley plastocyanin and azurin from Pseudomonas aeruginosa. No voltammetry was observed at the virgin electrodes, but signals were observed if the electrodes were anodised, or abraded with alumina, prior to use. Plastocyanin, which has a considerable overall negative charge and a surface acidic patch which is important in forming a productive electron transfer complex with its redox partners, gave a faradaic signal at pre-treated BDD only in the presence of neomycin, a positively charged polyamine. The voltammetry of azurin, which has a small overall charge and no surface acidic patch, was obtained identically in the presence and absence of neomycin. Investigations were also carried out into the voltammetry of two site-directed mutants of azurin, M64E azurin and M44K azurin, each of which introduce a charge into the protein's surface hydrophobic patch. The oxidizing and cleaning effects of the BDD electrode pre-treatments were studied electrochemically using two inorganic probe ions, Fe(China) 6 3- and Ru(NH 3 ) 6 3+ , and by X-ray photoelectron spectroscopy (XPS). All of the electrochemical results are discussed in relation to the electrostatic and hydrophobic contributions to the protein/diamond electrochemical interaction

  14. Introduction of gold nanoparticles into myoglobin-Nafion film for direct electrochemistry application.

    Science.gov (United States)

    Xie, Wenting; Kong, Linlin; Kan, Meixiu; Han, Dongmei; Wang, Xueji; Zhang, Hui-Min

    2010-10-01

    An effective myoglobin-Nafion film is prepared by introducing gold nanoparticles in through a simple procedure by ion-exchange combined with electrochemical reduction. Gold nanoparticles are highly dispersed in myoglobin-Nafion film with an average size of 2.3 +/- 0.2 nm. The electrochemical behavior of myoglobin entrapped in the film has been carefully investigated with cyclic voltammetry. The results show that the introduction of gold nanoparticles into myoglobin-Nafion film makes the direct electron transfer of myoglobin efficient. A pair of well-defined redox peaks for myoglobin heme Fe(II)/Fe(III) is observed with a formal potential of -0.150 V in 0.1 M phosphate buffer (pH 7.0). The electrochemical parameters of myoglobin in the composite film are further calculated with the results of the electron-transfer rate constant (k(s)) as 0.93 s(-1) and the charge transfer coefficient (alpha) as 0.69. The experimental results also demonstrate that the immobilized myoglobin retains its electrocatalytic activity for the reduction of hydrogen peroxide and the catalytic reduction peak of myoglobin appear in a linear relationship with H2O2 concentration in the range of 10.0-235.0 microM with correlation coefficient of 0.9970. Thus fabricated Au/Mb/Nafion electrode should give a new approach for developing redox protein or enzyme-based biosensors.

  15. Clay-chitosan-gold nanoparticle nanohybrid: Preparation and application for assembly and direct electrochemistry of myoglobin

    International Nuclear Information System (INIS)

    Zhao Xiaojuan; Mai Zhibin; Kang Xinhuang; Dai Zong; Zou Xiaoyong

    2008-01-01

    A biocompatible nanohybrid material (clay/AuCS) based on clay, chitosan and gold nanoparticles was explored. The material could provide a favorable microenvironment for proteins to realize the direct electron transfer on glassy carbon electrodes (GCE). Myoglobin (Mb), as a model protein to investigate the nanohybrid, was immobilized between the clay/AuCS film and another clay layer. Mb in the system exhibited a pair of well-defined and quasi-reversible redox peaks at -0.160 V (vs. saturated Ag/AgCl electrode) in 0.1 M PBS (pH 7.0), corresponding to its heme Fe III /Fe II redox couples. UV-vis spectrum suggested that Mb retained its native conformation in the system. Basal plane spacing of clay obtained by X-ray diffraction (XRD) indicated that there was an intercalation-exfoliation-restacking process among Mb, AuCS and clay during the modified film drying. Excellent biocatalytic activity of Mb in the modified system was exemplified by the reduction of hydrogen peroxide and nitrite. The linear range of H 2 O 2 determination was from 3.9 x 10 -5 to 3.0 x 10 -3 M with a detection limit of 7.5 μM based on the signal to noise ratio of 3. The kinetic parameters such as α (charge transfer coefficient), k s (electron transfer rate constant) and K m (Michaelis-Menten constant) were evaluated to be 0.55, 2.66 ± 0.15 s -1 and 5.10 mM, respectively

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

    Energy Technology Data Exchange (ETDEWEB)

    Deng Kun; Xiang Yang; Zhang Liqun; Chen Qinghai [Laboratory of the Clinical Experimental Base of Biosensor and Microarray, Center of Molecule and Gene Diagnosis, Southwest Hospital, Third Military Medical University, Chongqing 400042 (China); Fu Weiling, E-mail: weilingfu@yahoo.com [Laboratory of the Clinical Experimental Base of Biosensor and Microarray, Center of Molecule and Gene Diagnosis, Southwest Hospital, Third Military Medical University, Chongqing 400042 (China)

    2013-01-08

    Highlights: Black-Right-Pointing-Pointer Direct electrochemistry of glucose oxidase used for signal generation in aptasensor. Black-Right-Pointing-Pointer Using novel nanocomposite for immobilization and signal amplification. Black-Right-Pointing-Pointer Sensitive electrochemical detection of platelet-derived growth factor. - Abstract: 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.

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

    International Nuclear Information System (INIS)

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

    2013-01-01

    Highlights: ► Direct electrochemistry of glucose oxidase used for signal generation in aptasensor. ► Using novel nanocomposite for immobilization and signal amplification. ► Sensitive electrochemical detection of platelet-derived growth factor. - Abstract: 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.

  18. Flower-like Bi2Se3 nanostructures: Synthesis and their application for the direct electrochemistry of hemoglobin and H2O2 detection

    International Nuclear Information System (INIS)

    Fan Hai; Zhang Shenxiang; Ju Peng; Su Haichao; Ai Shiyun

    2012-01-01

    Highlights: ► Flower-like Bi 2 Se 3 nanostructures were prepared via a hydrothermal technique. ► Bi 2 Se 3 nanostructures significantly improve the direct electron-transfer of Hb. ► The immobilized Hb shows high catalytic activity to the reduction of H 2 O 2 . - Abstract: In this paper, flower-like Bi 2 Se 3 nanostructures consisting of intercrossed nanosheets networks have been synthesized via a facile hydrothermal technique and applied to the protein electrochemistry for the first time. The prepared Bi 2 Se 3 nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The direct electrochemistry of hemoglobin (Hb) has been achieved by immobilizing Hb on the prepared Bi 2 Se 3 nanostructures and Nafion (Nf) modified glassy carbon electrode. Bi 2 Se 3 nanostructures show significant promotion to the direct electron-transfer of Hb. The immobilized Hb retained its biological activity well and shows high catalytic activity to the reduction of hydrogen peroxide (H 2 O 2 ). Under the optimal experimental conditions, the catalytic currents are linear to the concentrations of H 2 O 2 in the range of 2.0 × 10 −6 to 1.0 × 10 −4 M. The corresponding detection limits are 6.3 × 10 −7 M. The prepared flower-like Bi 2 Se 3 nanostructures provide an alternative matrix for protein immobilization and biosensor preparation.

  19. Direct electrochemistry of glucose oxidase and sensing glucose using a screen-printed carbon electrode modified with graphite nanosheets and zinc oxide nanoparticles

    International Nuclear Information System (INIS)

    Karuppiah, Chelladurai; Palanisamy, Selvakumar; Chen, Shen-Ming; Veeramani, Vediyappan; Periakaruppan, Prakash

    2014-01-01

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

  20. Modern aspects of electrochemistry

    CERN Document Server

    Vayenas, Constantinos G

    2007-01-01

    This book covers a broad range of topics in Electrochemistry in an authoritative manner by internationally renowned specialists. Topics include a chapter on the survey of experimental techniques and devices of solid state electrochemistry begun in Volume 39.

  1. Electrochemistry of technetium

    International Nuclear Information System (INIS)

    Russell, C.D.; Alabama Univ., Birmingham

    1982-01-01

    Recent work on the electrochemistry of technetium is reviewed, covering the period 1973-1980. Topics include polarographic studies of aqueous pertechnetate, coulometric studies of aqueous pertechnetate at mercury cathodes, and electrochemistry of pertechnetate at solid electrodes. A review is also given of electrochemistry of other technetium compounds, non-aqueous systems, chemical redox reactions, and substitution reactions. Consideration is also given to studies of electrochemistry at tracer concentrations, electrolytic syntheses, standard electrode potentials, and electroanalytical methods. (author)

  2. Protein Electrochemistry: Questions and Answers.

    Science.gov (United States)

    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.

  3. Direct electrochemistry of glucose oxidase and a biosensor for glucose based on a glass carbon electrode modified with MoS2 nanosheets decorated with gold nanoparticles

    International Nuclear Information System (INIS)

    Su, Shao; Sun, Haofan; Xu, Fei; Yuwen, Lihui; Wang, Lianhui; Fan, Chunhai

    2014-01-01

    An electrochemical glucose biosensor was developed by immobilizing glucose oxidase (GOx) on a glass carbon electrode that was modified with molybdenum disulfide (MoS 2 ) nanosheets that were decorated with gold nanoparticles (AuNPs). The electrochemical performance of the modified electrode was investigated by cyclic voltammetry, and it is found that use of the AuNPs-decorated MoS 2 nanocomposite accelerates the electron transfer from electrode to the immobilized enzyme. This enables the direct electrochemistry of GOx without any electron mediator. The synergistic effect the MoS 2 nanosheets and the AuNPs result in excellent electrocatalytic activity. Glucose can be detected in the concentration range from 10 to 300 μM, and down to levels as low as 2.8 μM. The biosensor also displays good reproducibility and long-term stability, suggesting that it represents a promising tool for biological assays. (author)

  4. Silicon: electrochemistry and luminescence

    NARCIS (Netherlands)

    Kooij, Ernst Stefan

    1997-01-01

    The electrochemistry of crystalline and porous silicon and the luminescence from porous silicon has been studied. One chapter deals with a model for the anodic dissolution of silicon in HF solution. In following chapters both the electrochemistry and various ways of generating visible

  5. Direct electrochemistry and electrocatalysis of hemoglobin at three-dimensional gold film electrode modified with self-assembled monolayers of 3-mercaptopropylphosphonic acid

    International Nuclear Information System (INIS)

    Chen Yu; Yang Xiaojing; Guo Lirong; Li Jing; Xia Xinghua; Zheng Limin

    2009-01-01

    Multilayered hemoglobin (Hb) molecules were successfully immobilized on three-dimensional gold film electrode modified with self-assembled monolayers (SAMs) of 3-mercaptopropylphosphonic acid. Direct electrochemistry of the immobilized multilayered Hb occurs with high thermal stability and electrochemical stability. In the multilayered Hb film, the most inner Hb molecules can directly transfer electron with the electrode, while the Hb protein beyond this layer communicates electron with the electrode via protein-protein electron exchange. In addition, the proposed functional interface can greatly enhance electron transfer rate of the immobilized Hb protein (k s = 15.8 ± 2.0 s -1 ) due to the increase of roughness of the gold substrate. Under optimized experimental conditions, the multilayered Hb film displays good bioelectrocatalytic activity toward the reduction of hydrogen peroxide. This electrochemical sensor shows fast response (less than 1 s), wide linear range (7.8 x 10 -8 to 9.1 x 10 -5 M) and low detection limit (2.5 x 10 -8 M), which can be attributed to good mass transport, large Hb proteins loading per unit area and fast electron transfer rate of Hb protein.

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

    Science.gov (United States)

    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.

  7. Fabrication of biomembrane-like films on carbon electrodes using alkanethiol and diazonium salt and their application for direct electrochemistry of myoglobin.

    Science.gov (United States)

    Anjum, Saima; Qi, Wenjing; Gao, Wenyue; Zhao, Jianming; Hanif, Saima; Aziz-Ur-Rehman; Xu, Guobao

    2015-03-15

    Alkanethiols generally form self-assembled monolayers on gold electrodes and the electrochemical reduction of aromatic diazonium salts is a popular method for the covalent modification of carbon. Based on the reaction of alkanethiol with aldehyde groups covalently bound on carbon surface by the electrochemical reduction of aromatic diazonium salts, a new strategy for the modification of carbon electrodes with alkanethiols has been developed. The modification of carbon surface with aldehyde groups is achieved by the electrochemical reduction of aromatic diazonium salts in situ electrogenerated from a nitro precursor, p-nitrophenylaldehyde, in the presence of nitrous acid. By this way, in situ electrogenerated p-aminophenyl aldehyde from p-nitrophenylaldehyde immediately reacts with nitrous acid, effectively minimizing the side reaction of amine groups and aldehyde groups. The as-prepared alkanethiol-modified glassy carbon electrode was further used to make biomembrane-like films by casting didodecyldimethylammonium bromide on its surface. The biomembrane-like films enable the direct electrochemistry of immobilized myoglobin for the detection of hydrogen peroxide. The response is linear over the range of 1-600μM with a detection limit of 0.3μM. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  10. Amperometric carbohydrate antigen 19-9 immunosensor based on three dimensional ordered macroporous magnetic Au film coupling direct electrochemistry of horseradish peroxidase

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Qi [College of Sciences, Nanjing Tech University, Nanjing 211816 (China); Chen, Xiaojun, E-mail: chenxj_njut@126.com [College of Sciences, Nanjing Tech University, Nanjing 211816 (China); State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009 (China); Tang, Yin [Zhangjiagang Hospital of Traditional Chinese Medicine, Zhangjiagang 215600 (China); Ge, Lingna; Guo, Buhua [College of Sciences, Nanjing Tech University, Nanjing 211816 (China); Yao, Cheng, E-mail: yaochengnjut@163.com [College of Sciences, Nanjing Tech University, Nanjing 211816 (China)

    2014-03-01

    Highlights: • Three dimensional ordered macroporous magnetic electrode was newly used in electrochemical immunosensor. • The large surface area of macroporous magnetic electrode could improve the immobilized amount of antibody. • Au nanoparticles functionalized SBA-15 was used to immobilize enzyme labeled Ab₂ and enzyme. • Macroporous magnetic electrode and Au nanoparticles composite facilitated the direct electron transfer of enzyme. • The immunoassay avoided adding electron transfer mediator, simplifying the procedure. Abstract: A sandwich-type electrochemical immunosensor for the detection of carbohydrate antigen 19-9 (CA 19-9) antigen based on the immobilization of primary antibody (Ab₁) on three dimensional ordered macroporous magnetic (3DOMM) electrode, and the direct electrochemistry of horseradish peroxidase (HRP) that was used as both the label of secondary antibody (Ab₂) and the blocking reagent. The 3DOMM electrode was fabricated by introducing core–shell Au–SiO₂@Fe₃O₄ nanospheres onto the surface of three dimensional ordered macroporous (3DOM) Au electrode via the application of an external magnet. Au nanoparticles functionalized SBA-15 (Au@SBA-15) was conjugated to the HRP labeled secondary antibody (HRP-Ab₂) through the Au–SH or Au–NH₃⁺ interaction, and HRP was also used as the block reagent. The formation of antigen–antibody complex made the combination of Au@SBA-15 and 3DOMM exhibit remarkable synergistic effects for accelerating direct electron transfer (DET) between HRP and the electrode. Under the optimal conditions, the DET current signal increased proportionally to CA 19-9 concentration in the range of 0.05 to 15.65 U mL⁻¹ with a detection limit of 0.01 U mL⁻¹. Moreover, the immunosensor showed high selectivity, good stability, satisfactory reproducibility and regeneration. Importantly, the developed method was used to assay clinical serum specimens, achieving a good relation with those obtained from

  11. Instrumental methods in electrochemistry

    CERN Document Server

    Pletcher, D; Peat, R

    2010-01-01

    Using 372 references and 211 illustrations, this book underlines the fundamentals of electrochemistry essential to the understanding of laboratory experiments. It treats not only the fundamental concepts of electrode reactions, but also covers the methodology and practical application of the many versatile electrochemical techniques available.Underlines the fundamentals of electrochemistry essential to the understanding of laboratory experimentsTreats the fundamental concepts of electrode reactionsCovers the methodology and practical application of the many ve

  12. Synthesis of 1,3-di(4-amino-1-pyridinium)propane ionic liquid functionalized graphene nanosheets and its application in direct electrochemistry of hemoglobin

    International Nuclear Information System (INIS)

    Li, Rui; Liu, Changxian; Ma, Ming; Wang, Zhengguo; Zhan, Guoqing; Li, Buhai; Wang, Xian; Fang, Huaifang; Zhang, Huijuan; Li, Chunya

    2013-01-01

    Highlights: ► 1,3-Di(4-amino-1-pyridinium)propane tetrafluoroborate ionic liquid was successfully synthesized. ► Ionic liquid modified graphene nanosheets were successfully prepared and fully characterized. ► Hb was immobilized on the as-prepared graphene–ionic liquid nanosheets. ► Direct electrochemistry of Hb was succeeded. ► Biocatalysis of Hb towards H 2 O 2 was demonstrated, and was used in H 2 O 2 determination. -- Abstract: 1,3-Di(4-amino-1-pyridinium)propane tetrafluoroborate (DAPPT) ionic liquid was successfully synthesized, and was used as a modifier to functionalize graphene nanosheets through covalent binding of amino groups and epoxy groups in an alkaline solution. The as-prepared graphene-DAPPT nanosheets (Gr-DAPPT) were confirmed with transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV/vis and FTIR spectroscopy. A biocompatible platform based on Gr-DAPPT was constructed for the immobilization of hemoglobin (Hb) through a cross-linking step with chitosan and glutaraldehyde. The direct electron transfer and bioelectrocatalytic reaction of Hb immobilized on Gr-DAPPT surface were achieved. A pair of reversible redox peaks of hemoglobin was observed, and bioelectrocatalytic activity toward the reduction of H 2 O 2 was also demonstrated, displaying a potential application for the fabrication of novel biosensors to sense H 2 O 2 . Such results indicated that Gr-DAPPT based interface would be a promising platform for biomacromolecular immobilization and biosensor preparation

  13. Direct electrochemistry of CueO and its mutants at residues to and near type I Cu for oxygen-reducing biocathode

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Y.; Kamitaka, Y. [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku (Japan); Kurose, S.; Kataoka, K.; Sakurai, T. [Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa (Japan); Tsujimura, S.; Kano, K.

    2009-02-15

    CueO, a multi-copper oxidase (MCO) occurring in Escherichia coli, catalyses a four-electron reduction of O{sub 2} in a direct electron transfer (DET) mechanism with very high electrocatalytic activity on carbon aerogel electrodes. However, the overpotential of CueO is greater than that in other MCOs. By understanding the redox properties of CueO, we attempted to reduce this overpotential. Direct electrochemistry of CueO on carbon aerogel electrodes showed a pair of redox waves derived from the type I (T1) Cu site with a redox potential (E {sup circle} {sup '} atop T1) of 0.28 V versus Ag vertical stroke AgCl at pH 5.0. Dependence of E {sup circle} {sup '} atop T1 on pH suggests the participation of proton transfer and acid-base equilibrium of some amino acid residue. The shape of the catalytic current is consistent with the T1 site being an inlet of electrons in the DET bioelectrocatalysis of O{sub 2}, in which case the overpotential could be reduced by shifting E {sup circle} {sup '} atop T1 towards the positive potential. To achieve this, we created mutants of CueO at M510, which is the axial ligand of the T1 Cu, and at D439, which forms a hydrogen bond with His443 coordinated with the T1 Cu. Two mutants, M510L and D439A, successfully reduced the overpotential. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  14. A novel platform of hemoglobin on core-shell structurally Fe{sub 3}O{sub 4}-Au nanoparticles and its direct electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Liu Yang; Han Ting; Chen Chao; Bao Ning; Yu Chunmei [Institute of Analytical Chemistry for Life Science, School of Public Health, Nantong University, Nantong 226019 (China); Gu Haiying, E-mail: hygu@ntu.edu.c [Institute of Analytical Chemistry for Life Science, School of Public Health, Nantong University, Nantong 226019 (China)

    2011-03-30

    Research highlights: {yields} In recent years, immobilization of biomolecule onto nanomaterials, which could be utilized in the investigation of biomolecule reactions and the preparations of the biosensors, has attracted much research attention. A novel platform, which hemoglobin (Hb) was immobilized on core-shell structurally Fe{sub 3}O{sub 4}/Au nanoparticles (simplified as Fe{sub 3}O{sub 4}-Au NPs) modified glassy carbon electrode (GCE), has been developed for fabricating the third biosensors in this paper. {yields} Magnetic NPs stand out because of their added properties. However, naked Fe{sub 3}O{sub 4} NPs are very sensitive to oxidation because of their high chemical reactivity and being prone to aggregate. Those defects limit their further applications. We presented a simple approach to synthesize Au modified Fe{sub 3}O{sub 4} NPs with core-shell structure, which was characterized by transmission electron microscopy, scanning electron microscope, energy dispersive spectra and UV-vis spectroscopy. {yields} The thermodynamics, dynamics and catalysis properties of Hb immobilized on Fe{sub 3}O{sub 4}-Au NPs were discussed by UV-visible spectrum, electrochemical impedance spectroscopy, electrochemical quartz crystal microbalance technique and cyclic voltammetry. The electrocatalytic behaviors of the immobilized Hb on Fe{sub 3}O{sub 4}-Au NPs were applied for the determination of hydrogen peroxide, oxygen and trichloroacetic acid. The possible functions of Fe{sub 3}O{sub 4} core and Au shell as a novel platform for achieving Hb direct electrochemistry were also discussed, respectively. - Abstract: A novel platform, which hemoglobin (Hb) was immobilized on core-shell structurally Fe{sub 3}O{sub 4}/Au nanoparticles (simplified as Fe{sub 3}O{sub 4}-Au NPs) modified glassy carbon electrode (GCE), has been developed for fabricating the third biosensors. Fe{sub 3}O{sub 4}-Au NPs, characterized using transmission electron microscope (TEM), scanning electron microscope

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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. This journal is © The Royal Society of Chemistry 2012

  18. Direct electrochemistry of glucose oxidase on novel free-standing nitrogen-doped carbon nanospheres@carbon nanofibers composite film.

    Science.gov (United States)

    Zhang, Xueping; Liu, Dong; Li, Libo; You, Tianyan

    2015-05-06

    We have proposed a novel free-standing nitrogen-doped carbon nanospheres@carbon nanofibers (NCNSs@CNFs) composite film with high processability for the investigation of the direct electron transfer (DET) of glucose oxidase (GOx) and the DET-based glucose biosensing. The composites were simply prepared by controlled thermal treatment of electrospun polypyrrole nanospheres doped polyacrylonitrile nanofibers (PPyNSs@PAN NFs). Without any pretreatment, the as-prepared material can directly serve as a platform for GOx immobilization. The cyclic voltammetry of immobilized GOx showed a pair of well-defined redox peaks in O2-free solution, indicating the DET of GOx. With the addition of glucose, the anodic peak current increased, while the cathodic peak current decreased, which demonstrated the DET-based bioelectrocatalysis. The detection of glucose based on the DET of GOx was achieved, which displayed high sensitivity, stability and selectivity, with a low detection limit of 2 μM and wide linear range of 12-1000 μM. These results demonstrate that the as-obtained NCNSs@CNFs can serve as an ideal platform for the construction of the third-generation glucose biosensor.

  19. Direct electrochemistry of hemoglobin and biosensing for hydrogen peroxide using a film containing silver nanoparticles and poly(amidoamine) dendrimer

    Energy Technology Data Exchange (ETDEWEB)

    Baccarin, Marina [Nanomedicine and Nanotoxicology Group, Instituto de Física de São Carlos, Universidade de São Paulo, 13566-390 São Carlos, SP (Brazil); Departamento de Química, Universidade Federal de São Carlos, 13565-970 São Carlos, SP (Brazil); Janegitz, Bruno C., E-mail: brunocj@ymail.com [Departamento de Química, Universidade Federal de São Carlos, 13565-970 São Carlos, SP (Brazil); Departamento de Ciências da Natureza, Matemática e Educação, Universidade Federal de São Carlos, 13600-970 Araras, SP (Brazil); Berté, Rodrigo [Nanomedicine and Nanotoxicology Group, Instituto de Física de São Carlos, Universidade de São Paulo, 13566-390 São Carlos, SP (Brazil); Vicentini, Fernando Campanhã [Departamento de Química, Universidade Federal de São Carlos, 13565-970 São Carlos, SP (Brazil); Banks, Craig E. [Faculty of Science and Engineering, School of Chemistry and the Environment, Division of Chemistry and Environmental Science, Manchester Metropolitan University, Chester Street, Manchester M15GD (United Kingdom); Fatibello-Filho, Orlando [Departamento de Química, Universidade Federal de São Carlos, 13565-970 São Carlos, SP (Brazil); and others

    2016-01-01

    A new architecture for a biosensor is proposed using a glassy carbon electrode (GCE) modified with hemoglobin (Hb) and silver nanoparticles (AgNPs) encapsulated in poly(amidoamine) dendrimer (PAMAM). The biosensors were characterized using ultraviolet–visible spectroscopy, ζ-potential and cyclic voltammetry to investigate the interactions between Hb, AgNPs and the PAMAM film. The biosensor exhibited a well-defined cathodic peak attributed to reduction of the Fe{sup 3+} present in the heme group in Hb, as revealed by cyclic voltammetry in the presence of O{sub 2}. An apparent heterogeneous electron transfer rate of 4.1 s{sup −1} was obtained. The Hb–AgNPs-PAMAM/GCE third generation biosensor was applied in the amperometric determination of hydrogen peroxide over the linear range from 6.0 × 10{sup −6} to 9.1 × 10{sup −5} mol L{sup −1} with a detection limit of 4.9 × 10{sup −6} mol L{sup −1}. The proposed method can be extended to immobilize and evaluate the direct electron transfer of other redox enzymes. - Highlights: • A new architecture for biosensor using Hb, AgNPs and PAMAM is proposed. • H{sub 2}O{sub 2} is determined by amperometry using the proposed third generation biosensor. • The direct electron transfer was obtained from Hb using Hb–AgNPs–PAMAM.

  20. Direct electrochemistry of hemoglobin and biosensing for hydrogen peroxide using a film containing silver nanoparticles and poly(amidoamine) dendrimer

    International Nuclear Information System (INIS)

    Baccarin, Marina; Janegitz, Bruno C.; Berté, Rodrigo; Vicentini, Fernando Campanhã; Banks, Craig E.; Fatibello-Filho, Orlando

    2016-01-01

    A new architecture for a biosensor is proposed using a glassy carbon electrode (GCE) modified with hemoglobin (Hb) and silver nanoparticles (AgNPs) encapsulated in poly(amidoamine) dendrimer (PAMAM). The biosensors were characterized using ultraviolet–visible spectroscopy, ζ-potential and cyclic voltammetry to investigate the interactions between Hb, AgNPs and the PAMAM film. The biosensor exhibited a well-defined cathodic peak attributed to reduction of the Fe"3"+ present in the heme group in Hb, as revealed by cyclic voltammetry in the presence of O_2. An apparent heterogeneous electron transfer rate of 4.1 s"−"1 was obtained. The Hb–AgNPs-PAMAM/GCE third generation biosensor was applied in the amperometric determination of hydrogen peroxide over the linear range from 6.0 × 10"−"6 to 9.1 × 10"−"5 mol L"−"1 with a detection limit of 4.9 × 10"−"6 mol L"−"1. The proposed method can be extended to immobilize and evaluate the direct electron transfer of other redox enzymes. - Highlights: • A new architecture for biosensor using Hb, AgNPs and PAMAM is proposed. • H_2O_2 is determined by amperometry using the proposed third generation biosensor. • The direct electron transfer was obtained from Hb using Hb–AgNPs–PAMAM.

  1. Direct electrochemistry of glucose oxidase immobilized on nanostructured gold thin films and its application to bioelectrochemical glucose sensor

    International Nuclear Information System (INIS)

    Qiu Cuicui; Wang Xia; Liu Xueying; Hou Shifeng; Ma Houyi

    2012-01-01

    Highlights: ► Au thin films are formed by electrodeposition and galvanic replacement technology. ► Glucose oxidase is stably immobilized via a simple physical adsorption method. ► The direct electrochemical behavior is obtained on the immobilized glucose oxidase. ► An amperometric sensor of glucose with an excellent sensing capability is achieved. - Abstract: Glucose oxidase (GOx) was stably immobilized via a simple physical adsorption method onto the nanostructured Au thin films fabricated by using electrodeposition and galvanic replacement technology, which provides a facile method to prepare morphology-controllable Au films and also facilitates the preparation and application of enzyme modified electrodes. An obvious advantage of the as-prepared enzyme electrode (denoted as GOx/Au/GCE) is that the nano-Au films provide a favorable microenvironment for GOx and facilitate the electron transfer between the active center of GOx and electrodes. Cyclic voltammetry (CV) results indicate that the immobilized GOx displayed a direct, reversible and surface-confined redox reaction in the phosphate buffer solution. Furthermore, the enzyme modified electrode was used as a glucose bioelectrochemical sensor, exhibiting a linear relationship in the concentration ranges of 2.5–32.5 μmol L −1 and 60–130 μmol L −1 with a detection limit of 0.32 μmol L −1 (S/N = 3) at an applied potential of −0.55 V. Due to the excellent stability, sensitivity and anti-interference ability, the Au thin films are hopeful in the construction of glucose biosensors.

  2. Electrochemistry - variety from volts

    Energy Technology Data Exchange (ETDEWEB)

    Spurgeon, D.

    1985-07-01

    At a UNESCO conference held in Paris, France in June 1984 to honor Alessandro Volta, many experts maintained that electrochemistry holds much promise for the developing countries because many of its processes are inexpensive, simple, and easily adapted to the materials and conditions of the developing world. Some of the uses of electrochemistry highlighted at the conference, already available or imminent include: semiconductors in photoelectrochemical cells; photoelectrochemical systems for carrying out chemical reaction; electrophoretic deposition of paints or plastic coatings; electrochemical machining; quantitative analysis of chemicals, and diagnostics of brain chemistry.

  3. Self-assembly of glucose oxidase on reduced graphene oxide-magnetic nanoparticles nanocomposite-based direct electrochemistry for reagentless glucose biosensor.

    Science.gov (United States)

    Pakapongpan, Saithip; Poo-Arporn, Rungtiva P

    2017-07-01

    A novel approach of the immobilization of a highly selective and stable glucose biosensor based on direct electrochemistry was fabricated by a self-assembly of glucose oxidase (GOD) on reduced graphene oxide (RGO) covalently conjugated to magnetic nanoparticles (Fe 3 O 4 NPs) modified on a magnetic screen-printed electrode (MSPE). The RGO-Fe 3 O 4 nanocomposite has remarkable enhancement in large surface areas, is favorable environment for enzyme immobilization, facilitates electron transfer between enzymes and electrode surfaces and possesses superparamagnetism property. The morphology and electrochemical properties of RGO-Fe 3 O 4 /GOD were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, cyclic voltammetry (CV) and amperometry. The modified electrode was a fast, direct electron transfer with an apparent electron transfer rate constant (k s ) of 13.78s -1 . The proposed biosensor showed fast amperometric response (3s) to glucose with a wide linear range from 0.05 to 1mM, a low detection limit of 0.1μM at a signal to noise ratio of 3 (S/N=3) and good sensitivity (5.9μA/mM). The resulting biosensor has high stability, good reproducibility, excellent selectivity and successfully applied detection potential at -0.45V. This mediatorless glucose sensing used the advantages of covalent bonding and self-assembly as a new approach for immobilizing enzymes without any binder. It would be worth noting that it opens a new avenue for fabricating excellent electrochemical biosensors. This is a new approach that reporting the immobilization of glucose oxidase on reduced graphene oxide (RGO) covalently conjugated to magnetic nanoparticles (Fe 3 O 4 NPs) by electrostatic interaction and modified screen printed electrode. We propose the reagentless with fabrication method without binder and adhesive agents for immobilized enzyme. Fe 3 O 4 NPs increasing surface area to enhance the immobilization and prevent

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

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Wei, E-mail: swyy26@hotmail.com [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 China (China); College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Cao, Lili; Deng, Ying; Gong, Shixing [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Shi, Fan; Li, Gaonan; Sun, Zhenfan [College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158 China (China)

    2013-06-05

    Graphical abstract: -- Highlights: •A graphene and multi-walled carbon nanotubes nanocomposite was prepared. •Hemoglobin and nanocomposite modified carbon ionic liquid electrode was fabricated. •Direct electrochemistry of hemoglobin was realized on the modified electrode. •Bioelectrocatalysis towards the reduction of different substrates was enhanced. -- Abstract: 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 (k{sub s}) as 0.97 s{sup −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{sup −1} with a detection limit of 0.0153 mmol L{sup −1} (3σ), H{sub 2}O{sub 2} in the concentration range from 0.1 to 516.0 mmol L{sup −1} with a detection limit of 34.9 nmol/L (3σ) and NaNO{sub 2} in the concentration range from 0.5 to 650.0 mmol L{sup −1} with a detection limit of 0

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

    International Nuclear Information System (INIS)

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

    2013-01-01

    Graphical abstract: -- Highlights: •A graphene and multi-walled carbon nanotubes nanocomposite was prepared. •Hemoglobin and nanocomposite modified carbon ionic liquid electrode was fabricated. •Direct electrochemistry of hemoglobin was realized on the modified electrode. •Bioelectrocatalysis towards the reduction of different substrates was enhanced. -- Abstract: 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 (k s ) 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), H 2 O 2 in the concentration range from 0.1 to 516.0 mmol L −1 with a detection limit of 34.9 nmol/L (3σ) and NaNO 2 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

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

    Science.gov (United States)

    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.

  7. Preparation and characterization of room temperature ionic liquid/single-walled carbon nanotube nanocomposites and their application to the direct electrochemistry of heme-containing proteins/enzymes

    International Nuclear Information System (INIS)

    Du, Pan; Liu, Shuna; Wu, Ping; Cai, Chenxin

    2007-01-01

    This work describes the formation and possible electrochemical application of a novel nanocomposite based on single-walled carbon nanotubes (SWNTs) and imidazolium-based room-temperature ionic liquids (RTILs) of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF 4 , a hydrophilic RTIL) and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF 6 , a hydrophobic RTIL). The nanocomposites ([bmim]BF 4 -SWNTs, and [bmim]PF 6 -SWNTs) were formed by simply grinding the SWNTs with the respective RTIL. The results of the X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy indicated that the nanocomposites were formed by adsorption of an imidazolium ion on the surface of SWNTs via the 'cation-π' interaction. SEM images showed that [bmim]BF 4 -SWNTs (or [bmim]PF 6 -SWNTs) nanocomposites could uniformly cover the surface of a glassy carbon (GC) electrode resulting in a RTILs-SWNTs/GC modified electrode with a high stability. The RTILs-SWNTs composite could be readily used as a matrix to immobilize heme-containing proteins/enzymes (myoglobin, cytochrome c, and horseradish peroxidase) without undergoing denaturation, as was verified by UV-vis and circular dichroic (CD) spectroscopic results. The voltammetric results showed that heme-containing proteins/enzymes entrapped in RTILs-SWNTs composites displayed a pair of well-defined, stable redox peaks, which were ascribed to their direct electron-transfer reactions. The results of controlled experiments showed that the positive charged imidazolium ion played a significant effect on the electrochemical parameters, such as the redox peak separation and the value of the formal potentials, etc., of the electron-transfer reaction of non-neutral species dissolved in solution or immobilized on the electrode surface. Further results demonstrated that the heme-containing proteins/enzymes entrapped in RTILs-SWNTs composites could still retain their bioelectrocatalytic activity toward the reduction of oxygen and hydrogen

  8. Nanocrystalline TiO{sub 2} films containing sulfur and gold: Synthesis, characterization and application to immobilize and direct electrochemistry of cytochrome c

    Energy Technology Data Exchange (ETDEWEB)

    Rafiee-Pour, Hossain-Ali, E-mail: rafieepour@kashanu.ac.ir [Biotechnology Division, Department of Molecular and Cell Biology, Faculty of Chemistry, University of Kashan, Kashan, Islamic Republic of Iran (Iran, Islamic Republic of); Hamadanian, Masood [Institute of Nanoscience and Nanotechnology, University of Kashan, Kashan , Islamic Republic of Iran (Iran, Islamic Republic of); Department of Physical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Islamic Republic of Iran (Iran, Islamic Republic of); Koushali, Samaneh Katebi [Department of Physical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Islamic Republic of Iran (Iran, Islamic Republic of)

    2016-02-15

    Graphical abstract: - Highlights: • Promoting efficiency of TiO{sub 2} in cyt c immobilization by metal and nonmetal doping. • Synthesis of Au/S-TiO{sub 2} as a novel and efficient for cyt c immobilization. • Investigating structural, chemical and morphological characteristics of prepared TiO{sub 2}, S-TiO{sub 2} and Au/S-TiO{sub 2} nanoparticles. • 4%Au/S-TiO{sub 2} showed high surface area, nanometer size, strong absorbance, high efficiency in cyt c immobilization. • Promoting immobilization efficiency by addition of a small amount of gold at the surface of TiO{sub 2} by photochemistry method. - Abstract: In this paper, nanoporous titanium dioxide (TiO{sub 2}) 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 [E{sup 0}′ = (E{sub pa} + E{sub pc})/2] of 53 mV versus Ag/AgCl). In addition the effect of metal and nonmetal ions (Au, S) co-doping on the efficiency of TiO{sub 2} 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 TiO{sub 2} (Au/S-TiO{sub 2}) with a spheroidal shape demonstrates a smaller grain size than the pure TiO{sub 2}. Meanwhile, the UV–vis DRS of Au/S-TiO{sub 2} showed a considerable red shift to the visible region. As a result, it was found that 4% Au/0.1% S-TiO{sub 2} had the highest efficiency for cytochrome c immobilization. The results showed that the peak currents were higher after the annealing of the TiO{sub 2} film. This observation suggests that the use of TiO{sub 2} films may be advantageous for the development of nanoporous biosensors employing reductive electrochemistry.

  9. Electrochemistry and energy science

    International Nuclear Information System (INIS)

    Vijh, A.K.

    1980-01-01

    The purpose of the paper is to delineate the structure of moder electrochemistry and to elucidate the manner in which electrochemical ideas and techniques contribute to the development of power sources and the the advancement of energy science. One example of such an application is the prevention of corrosion in the coolant circuit of a nuclear power station, or its decontamination; another is the use of electrolysis for final upgrading of heavy water. (N.D.H.)

  10. Electrochemistry of isopolytungstate mixtures

    International Nuclear Information System (INIS)

    Borzenko, M.I.; Botukhova, G.N.; Tsirlina, G.A.; Petrii, O.A.

    2008-01-01

    Solutions of isopolytungstates are of interest as the precursors for electrodeposited rechargeable tungsten oxides, and also in relation to hydrogen evolution catalysis. Understanding of isopolytungstate electrochemistry is complicated by numerous pH-dependent equilibria. This paper presents some data of dc polarography and UV absorption spectroscopy for solutions always containing several types of coexisting isopolytungstate species, in order to understand the individual electrochemical reactivity of certain isopolyanions

  11. Size effects in electrochemistry

    International Nuclear Information System (INIS)

    Petrii, Oleg A; Tsirlina, Galina A

    2001-01-01

    General characteristics of size-dependent phenomena in electrochemical systems are given. Primary attention is paid to methodical achievements of nanoelectrochemistry, which is a line of research created over the last 15 years. The development of the main concepts of electrochemistry initiated by the stream of nanoscopic information is considered. The prospects for local studies of processes on charged interfaces, elementary steps of these processes and application of nanoelectrodes and related systems in interdisciplinary fields are discussed. The bibliography includes 198 references.

  12. Applications of electrochemistry in medicine

    CERN Document Server

    Schlesinger, Mordechay

    2013-01-01

    Medical Applications of Electrochemistry, a volume of the series Modern Aspects of Electrochemistry, illustrates the interdisciplinary nature of modern science by indicating the many current issues in medicine that are susceptible to solution by electrochemical methods. This book also suggests how personalized medicine can develop.

  13. Condensed matter physics in electrochemistry

    International Nuclear Information System (INIS)

    Kornyshev, A.A.

    1991-01-01

    Some topics in electrochemistry are considered from the condensed matter physics viewpoint in relation to the problems discussed in this book. Examples of the successful application of condensed matter physics to electrochemistry are discussed together with prospective problems and pressing questions. (author). 127 refs, 4 figs

  14. Applied Electrochemistry of Aluminum

    DEFF Research Database (Denmark)

    Li, Qingfeng; Qiu, Zhuxian

    Electrochemistry of aluminum is of special importance from both theoretical and technological point of view. It covers a wide range of electrolyte systems from molten fluoride melts at around 1000oC to room temperature molten salts, from aqueous to various organic media and from liquid to solid...... electrolytes. The book is an updated review of the technological advances in the fields of electrolytic production and refining of metals, electroplating, anodizing and other electrochemical surface treatments, primary and secondary batteries, electrolytic capacitors; corrosion and protection and others....

  15. Electrochemistry and Storage

    Science.gov (United States)

    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.

  16. Electrochemistry in supercritical fluids

    Science.gov (United States)

    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

  17. DNA-Mediated Electrochemistry

    Science.gov (United States)

    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

  18. 11. SIBEE: Brazilian symposium on electrochemistry and electro analytics

    International Nuclear Information System (INIS)

    1999-01-01

    Theoretical and experimental papers are presented in these proceedings on the following subjects: fundamental electrochemistry, energy electrochemical conversion, electro catalysis, corrosion, polymers, molecular electrochemistry and bio electrochemistry

  19. Students' understandings of electrochemistry

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

  1. Solved problems in electrochemistry

    International Nuclear Information System (INIS)

    Piron, D.L.

    2004-01-01

    This book presents calculated solutions to problems in fundamental and applied electrochemistry. It uses industrial data to illustrate scientific concepts and scientific knowledge to solve practical problems. It is subdivided into three parts. The first uses modern basic concepts, the second studies the scientific basis for electrode and electrolyte thermodynamics (including E-pH diagrams and the minimum energy involved in transformations) and the kinetics of rate processes (including the energy lost in heat and in parasite reactions). The third part treats larger problems in electrolysis and power generation, as well as in corrosion and its prevention. Each chapter includes three sections: the presentation of useful principles; some twenty problems with their solutions; and, a set of unsolved problems

  2. Synthetic diamond in electrochemistry

    International Nuclear Information System (INIS)

    Pleskov, Yurii V

    1999-01-01

    The results of studies on the electrochemistry of diamond carried out during the last decade are reviewed. Methods for the preparation, the crystalline structure and the main electrophysical properties of diamond thin films are considered. Depending on the doping conditions, the diamond behaves as a superwide-gap semiconductor or as a semimetal. It is shown that the 'metal-like' diamond is corrosion-resistant and can be used advantageously as an electrode in the electrosynthesis (in particular, for the electroreduction of compounds that are difficult to reduce) and electroanalysis. Kinetic characteristics of some redox reactions and the impedance parameters for diamond electrodes are presented. The results of comparative studies of the electrodes made of diamond single crystals, polycrystalline diamond and amorphous diamond-like carbon, which reveal the effect of the crystalline structure (e.g., the influence of intercrystallite boundaries) on the electrochemical properties of diamond, are presented. The bibliography includes 99 references.

  3. Folds and Etudes

    Science.gov (United States)

    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…

  4. Electrochemistry and microsystems

    International Nuclear Information System (INIS)

    Ehrfeld, Wolfgang

    2003-01-01

    Electrochemistry takes a key position in products and manufacturing processes of microtechnology, which has established a multi-billion dollar market with applications in information, entertainment, medical, automotive, telecom and many other technologies. In combination with microlithographic pattern generation electrochemical deposition processes are applied in manufacturing CDs and DVDs, nozzle plates for ink jet printers, read-write heads for hard magnetic disks and solder bumps for flip-chip technology. Three-dimensional microstructures with extremely high precision and aspect ratio are manufactured by means of LIGA technology, which combines deep lithography, electroforming and moulding process steps. Field assisted etching processes with ultra-short voltage pulses, anodization of silicon and field assisted ion exchange in glass have been successfully used for generating microstructures. Meanwhile, there are a huge number of microdevices, which utilize electrochemical phenomena. ISFETs and ion sensitive electrodes are standard components in the field of microsensors, microfuel cells will become high-performance power supply systems for mobile IT and entertainment products. In communication technology electrophoresis-based on electronic ink displays will become more and more important products. The most challenging development is dealing with so-called labs-on-a-chip which utilize electrochemical phenomena like electrophoresis, isoelectric focussing and electroosmosis to create a novel platform for ultra-miniaturized analytics in life sciences, medical diagnosis, environmental technologies and many other areas of modern development

  5. Electrochemistry and dye-sensitized solar cells

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav

    2017-01-01

    Roč. 2, č. 1 (2017), s. 88-98 ISSN 2451-9103 R&D Projects: GA ČR GA13-07724S Institutional support: RVO:61388955 Keywords : electrochemistry * dye-sensitized cells * photoelectrode Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

  6. Fundamentals and applications of electrochemistry

    Science.gov (United States)

    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.

  7. Electrochemistry in fast reactor technology

    International Nuclear Information System (INIS)

    Mathews, C.K.

    1987-01-01

    Electrochemistry plays a significant role in the production, characterisation or behaviour of the fuel, the coolant and structural materials used in fast reactor systems. The role of electrochemistry in sodium production, in the fuel cycle, in the development of electrochemical meters used for the on-line monitoring of the various impurities at sub ppm levels and in the recovery of plutonium and uranium are discussed. The advantage of voltammmetric techniques in the analysis of impurities and the application of electrochemical meters have been investigated. (author). 5 figs., 15 refs

  8. Detailed H2 and CO Electrochemistry for a MEA Model Fueled by Syngas

    KAUST Repository

    Lee, W. Y.; Ong, K. M.; Ghoniem, A. F.

    2015-01-01

    © The Electrochemical Society. SOFCs can directly oxidize CO in addition to H2, which allows them to be coupled to a gasifier. Many membrane-electrode-assembly (MEA) models neglect CO electrochemistry due to sluggish kinetics and the water

  9. The birth of protein electrochemistry.

    Science.gov (United States)

    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.

    Science.gov (United States)

    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. Copyright © 2012 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

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

    NARCIS (Netherlands)

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

    2016-01-01

    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

  12. National symposium on electrochemistry in nuclear technology

    International Nuclear Information System (INIS)

    1994-01-01

    A National Symposium on Electrochemistry in Nuclear Technology (NASENT-94) was held at Kalpakkam, India during January 5-7, 1994. The subjects covered a wide range of topics in electrochemistry, such as electrochemical production, refining, analysis and corrosion of metals, electrochemical monitors and sensors, solid state electrochemistry, applications of electrochemical processes and measurement techniques in nuclear technology etc. Papers relevant to INIS are indexed separately

  13. Dictionary of electrochemistry. Lexikon Elektrochemie

    Energy Technology Data Exchange (ETDEWEB)

    Hibbert, D B; James, A M

    1987-01-01

    Electrochemistry, officially a branch of physical chemistry, is an interdisciplinary field bordering on biology, physics, metallurgy and other fields of engineering. This glossary and dictionary presents information and basic knowledge on recent developments in electrochemistry, i.e. fuel cells, corrosion, energy conversion, electrode kinetics, ion-selective electrodes, and bioelectrochemistry. The user is given a short and precise definition of each term, its importance in different fields of science and, in case of measuring units, a description of the method of measurement. Electrochemical and thermodynamic equations are presented without formal proof, but with an indication of their applications and limitations. Access to relevant information is facilitated by drawings and tables. Bibliographic data are many, and SI units are used throughout the book. A dictionary in the annex makes it easier for the user to find English-language literature. The book may be a useful reference book for biologists, microbiologists, biochemists, chemists, pharmacists, geologists, physicists, technicians, and especially metallurgists.

  14. Electrochemistry. The basics, with examples

    Energy Technology Data Exchange (ETDEWEB)

    Lefrou, Christine [LEPMI, Saint Martin d' Heres (France); Poignet, Jean-Claude; Fabry, Pierre

    2012-07-01

    This book offers original and new approaches to the teaching of electrochemical concepts, principles and applications. Throughout the text the authors provide a balanced coverage of the thermodynamic and kinetic processes at the heart of electrochemical systems. The first half of the book outlines fundamental concepts appropriate to undergraduate students and the second half gives an in-depth account of electrochemical systems suitable for experienced scientists and course lecturers. Concepts are clearly explained and mathematical treatments are kept to a minimum or reported in appendices. This book features: 1. Questions and answers for self-assessment 2. Basic and advanced level numerical descriptions. 3. Illustrated electrochemistry applications This book is accessible to both novice and experienced electrochemists and supports a deep understanding of the fundamental principles and laws of electrochemistry.

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

    Science.gov (United States)

    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.

  16. Direct electrochemistry and electrocatalysis of myoglobin using an ionic liquid-modified carbon paste electrode coated with Co3O4 nanorods and gold nanoparticles

    International Nuclear Information System (INIS)

    Wang, Xiaofeng; You, Zheng; Sha, Hailiang; Gong, Shixing; Niu, Qingjuan; Sun, Wei

    2014-01-01

    A nanohybrid biomaterial was fabricated by mixing Co 3 O 4 nanorods, gold nanoparticles (Au-NPs) and myoglobin (Mb), and depositing it on the surface of a carbon paste electrode containing the ionic liquid N-hexylpyridinium hexafluorophosphate as the binder. UV–vis and FT-IR revealed the Mb in the composite film to have remained in its native structure. A pair of well-defined redox peaks appears in cyclic voltammograms and indicates direct electron transfer from the Mb to the underlying electrode. The results are attributed to the favorable orientation of Mb in the composite film, to the synergistic effects of Co 3 O 4 nanorods and Au-NPs. The modified electrode shows excellent electrocatalytic ability towards the reduction of substrates such as trichloroacetic acid and nitrite, and displays good stability and reproducibility. (author)

  17. A novel biosensor based on the direct electrochemistry of horseradish peroxidase immobilized in the three-dimensional flower-like Bi_2WO_6 microspheres

    International Nuclear Information System (INIS)

    Liu, Hui; Guo, Kai; Duan, Congyue; Chen, Xianjin; Zhu, Zhenfeng

    2016-01-01

    Three-dimensional flower-like Bi_2WO_6 microspheres (3D-Bi_2WO_6 MSs) have been synthesized through a simple hydrothermal method. The morphology and structure of 3D-Bi_2WO_6 MSs were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The 3D-Bi_2WO_6 MSs subsequently were used to immobilize horseradish peroxidase (HRP) and fabricate a mediator-free biosensor for the detection of H_2O_2. Spectroscopic and electrochemical results reveal that 3D-Bi_2WO_6 MSs constitute an excellent immobilization matrix with biocompatibility for enzymes. Meanwhile, due to unique morphology of the flower-like microspheres, the direct electron transfer of HRP is facilitated and the prepared biosensors display good performances for the detection of H_2O_2 with a wide linear range, including two linear sections: 0.5–100 μM (R"2 = 0.9983) and 100–250 μM (R"2 = 0.9981), as well as an extremely low method detection limit of 0.18 μM. - Highlights: • 3D-Bi_2WO_6 microspheres are used to fabricate a mediator-free biosensor firstly. • The biosensor displays a wide linear range of 0.5–250 μM for H_2O_2. • The biosensor exhibits a low detection limit of 0.18 μM for H_2O_2.

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

    Science.gov (United States)

    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 (RSDsascorbic acid and uric acid. The CAT/ChOx/GR-IL/GCE showed excellent analytical performance for the determination of free cholesterol in human serum samples. © 2013 Elsevier B.V. All rights reserved.

  19. Immobilization of glucose oxidase onto a novel platform based on modified TiO{sub 2} and graphene oxide, direct electrochemistry, catalytic and photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Haghighi, Nasibeh, E-mail: Haghighi.nasibeh@yahoo.com [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Hallaj, Rahman, E-mail: Rhallaj@uok.ac.ir [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Nanotechnology Research Center, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Salimi, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Nanotechnology Research Center, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2017-04-01

    In this work a new organic–inorganic nanocomposite has been introduced for enzyme immobilization. The composite consisting of graphene oxide (GO) and titanium oxide nanoparticles (TiO{sub 2}) modified with 2, 2′-dithioxo-3, 3′-bis (3-(triethoxysilyl) propyl)-2H, 2′H-[5, 5′-bithiazolylidene]-4, 4′(3H, 3′H)-dione as Organic-Inorganic Supporting Ligand (OISL). The OISL was covalently attached to TiO{sub 2} nanoparticles and employed for obtaining a suitable solid surface to enzyme attachment. The glucose oxidase (GOD) was irreversibly loaded on the GC/GO/TiO{sub 2}-OISL using consecutive cyclic voltammetry. The enzyme immobilization and the enzymatic activity were determined by electrochemical methods. The cyclic voltammogram displayed a pair of well-defined and nearly symmetric redox peaks with a formal potential of − 0.465 V and an apparent electron transfer rate constant of 1.74 s{sup −1}. The GO/TiO{sub 2}-OISL can catalyze the electroreduction and electrooxidation of hydrogen peroxide. The GC/GO/TiO{sub 2}-OISL/GOD electrode was used in the hydrogen peroxide determination. The fabricated nanobiocomposite shows dramatic photoelectrocatalytic activity which evaluated by studying the electrocatalytic activity of the fabricated electrode toward hydrogen peroxide in darkness and in the presences of light. - Highlights: • In this work a novel platform used to successful immobilization of glucose oxidase. Due to its large functional group this modified nanoparticles load enzyme (GOD) and remain enzyme whit out denaturation for a long time. • The loaded enzyme shows direct electron transfer and excellent charge transfer kinetic. Also the fabricated nano-bio-composite has good catalytic activity toward hydrogen peroxide during electrooxidation and electro reduction process. • The nano-bio-composite shows excellent photocatalytic activity.

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

    International Nuclear Information System (INIS)

    Haghighi, Nasibeh; Hallaj, Rahman; Salimi, Abdollah

    2017-01-01

    In this work a new organic–inorganic nanocomposite has been introduced for enzyme immobilization. The composite consisting of graphene oxide (GO) and titanium oxide nanoparticles (TiO 2 ) modified with 2, 2′-dithioxo-3, 3′-bis (3-(triethoxysilyl) propyl)-2H, 2′H-[5, 5′-bithiazolylidene]-4, 4′(3H, 3′H)-dione as Organic-Inorganic Supporting Ligand (OISL). The OISL was covalently attached to TiO 2 nanoparticles and employed for obtaining a suitable solid surface to enzyme attachment. The glucose oxidase (GOD) was irreversibly loaded on the GC/GO/TiO 2 -OISL using consecutive cyclic voltammetry. The enzyme immobilization and the enzymatic activity were determined by electrochemical methods. The cyclic voltammogram displayed a pair of well-defined and nearly symmetric redox peaks with a formal potential of − 0.465 V and an apparent electron transfer rate constant of 1.74 s −1 . The GO/TiO 2 -OISL can catalyze the electroreduction and electrooxidation of hydrogen peroxide. The GC/GO/TiO 2 -OISL/GOD electrode was used in the hydrogen peroxide determination. The fabricated nanobiocomposite shows dramatic photoelectrocatalytic activity which evaluated by studying the electrocatalytic activity of the fabricated electrode toward hydrogen peroxide in darkness and in the presences of light. - Highlights: • In this work a novel platform used to successful immobilization of glucose oxidase. Due to its large functional group this modified nanoparticles load enzyme (GOD) and remain enzyme whit out denaturation for a long time. • The loaded enzyme shows direct electron transfer and excellent charge transfer kinetic. Also the fabricated nano-bio-composite has good catalytic activity toward hydrogen peroxide during electrooxidation and electro reduction process. • The nano-bio-composite shows excellent photocatalytic activity.

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

    Science.gov (United States)

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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.

  3. Biomass electrochemistry : from cellulose to sorbitol

    NARCIS (Netherlands)

    Kwon, Youngkook

    2013-01-01

    The primary goal of this thesis is to study the potential role of electrochemistry in finding new routes for sustainable chemicals from biomass in aqueous-phase solutions. In order to assess the potential of electrochemistry in biomass conversion, we developed an online HPLC system by using a

  4. Factors that Prevent Learning in Electrochemistry

    Science.gov (United States)

    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…

  5. Study of the permeability up-scaling by direct filtering of geostatistical model; Etude du changement d'echelle des permeabilites par filtrage direct du modele geostatistique

    Energy Technology Data Exchange (ETDEWEB)

    Zargar, G

    2005-10-15

    In this thesis, we present a new approach, which consists in directly up-scaling the geostatistical permeability distribution rather than the individual realizations. Practically, filtering techniques based on. the FFT (Fast Fourier Transform), allows us to generate geostatistical images, which sample the up-scaled distributions. In the log normal case, an equivalence hydraulic criterion is proposed, allowing to re-estimate the geometric mean of the permeabilities. In the anisotropic case, the effective geometric mean becomes a tensor which depends on the level of filtering used and it can be calculated by a method of renormalisation. Then, the method was generalized for the categorial model. Numerical tests of the method were set up for isotropic, anisotropic and categorial models, which shows good agreement with theory. (author)

  6. Study of the permeability up-scaling by direct filtering of geostatistical model; Etude du changement d'echelle des permeabilites par filtrage direct du modele geostatistique

    Energy Technology Data Exchange (ETDEWEB)

    Zargar, G.

    2005-10-15

    In this thesis, we present a new approach, which consists in directly up-scaling the geostatistical permeability distribution rather than the individual realizations. Practically, filtering techniques based on. the FFT (Fast Fourier Transform), allows us to generate geostatistical images, which sample the up-scaled distributions. In the log normal case, an equivalence hydraulic criterion is proposed, allowing to re-estimate the geometric mean of the permeabilities. In the anisotropic case, the effective geometric mean becomes a tensor which depends on the level of filtering used and it can be calculated by a method of renormalisation. Then, the method was generalized for the categorial model. Numerical tests of the method were set up for isotropic, anisotropic and categorial models, which shows good agreement with theory. (author)

  7. Electrochemistry of lunar rocks

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  9. An Effective Approach to Teaching Electrochemistry.

    Science.gov (United States)

    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)

  10. New materials for solid state electrochemistry

    International Nuclear Information System (INIS)

    Ferloni, P.; Consiglio Nazionale delle Ricerche, Pavia; Magistris, A.; Consiglio Nazionale delle Ricerche, Pavia

    1994-01-01

    Solid state electrochemistry is an interdisciplinary area, undergoing nowadays a fast development. It is related on the one hand to chemistry, and on the other hand to crystallography, solid state physics and materials science. In this paper structural and electrical properties of some families of new materials interesting for solid state electrochemistry are reviewed. Attention is focused essentially on ceramic and crystalline materials, glasses and polymers, displaying high ionic conductivity and potentially suitable for various applications in solid state electrochemical devices. (orig.)

  11. DNA Electrochemistry with Tethered Methylene Blue

    Science.gov (United States)

    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

  12. Electrochemistry and spectro-electrochemistry of dithizonatophenylmercury(II)

    International Nuclear Information System (INIS)

    Eschwege, Karel G. von; As, Lydia van; Swarts, Jannie C.

    2011-01-01

    Graphical abstract: Display Omitted Highlights: → CV and spectroelectrochemistry of dithizone and PhHgHDz, 3, is presented. → CV shows 3 has stable metal thioether (Hg-S-C), 1 oxidation and two reductions. → 3 is photochromic (t 1/2, relaxation = 1300 s). → Electrochemistry of ground and photo-activated 3 is identical. → Spectroelectrochemistry of 3 highlights electrochromism. - Abstract: The reactions between dithizone (H 2 Dz, (1)) or potassium dithizonate (K + HDz - , (2)) and phenylmercury(II) chloride gives PhHg(HDz), (3). Complex (3) is photochromic. In dichloromethane, the blue photo-exited state of (3) exhibits a first order relaxation process to regenerate the orange ground state with rate constant 0.00053 s -1 . The half life of this relaxation is ca. 1300 s. Electrochemically, on cyclic voltammetry time scale, the oxidations of (1) and (3) are different. A comparative voltammetric and spectro-electrochemical study of (1) and (3) in CH 2 Cl 2 containing 0.1 mol dm -3 [N( n Bu) 4 ][B(C 6 F 5 ) 4 ] revealed that the mercapto group of (1) can be oxidised in two one-electron transfer steps. A disulphide is first produced and then in a second oxidation step, HDz + is formed. In contrast, complex (3) shows only one ligand-based oxidation step. Upon complexation with phenylmercury the free mercaptan group of (1) becomes a stable 'metal thioether', Hg-S-C, which effectively prevents disulphide formation in (3) upon electrochemical oxidation. Both (1) and (3) shows two reduction steps. The electrochemical fingerprint of blue photo-excited (3) is identical to that of the orange ground state as no new functional groups are introduced upon irradiation; only bond rotation occurs. The different electronic spectra for each of the redox states of (3), obtained from spectro-electrochemical measurements, revealed that only the (3)/(3 - ) couple exhibits electrochromic properties.

  13. 7. International Frumkin Symposium. Basic electrochemistry for science and technology. Abstracts. Part 1

    International Nuclear Information System (INIS)

    2000-01-01

    Modern tendencies of development of electrochemistry as in regions of fundamental investigations so in applied directions are presented. Basic themes of reports presented are: charge transport in condensed media, interface fenomena and electric properties at low soluble substances with electrolyte solutions, structure and properties of charged interfaces, transport in electrochemical systems, problems of bioelectrochemistry [ru

  14. 7. International Frumkin Symposium. Basic electrochemistry for science and technology. Abstracts. Part 2

    International Nuclear Information System (INIS)

    2000-01-01

    Modern tendencies of development of electrochemistry as in regions of fundamental investigations so in applied directions are presented. Basic themes of reports presented are: electrocatalysis and electrosynthesis, batteries and supercapacitors, corrosion and electrodeposition, electrolytes and membranes, biosensors and electroanalysis, nanoelectrochemistry [ru

  15. Electrochemistry and Radioactive Wastes: A Scientific Overview

    Directory of Open Access Journals (Sweden)

    Maher Abed Elaziz

    2015-12-01

    Full Text Available Radioactive wastes are arising from nuclear applications such as nuclear medicine and nuclear power plants. Radioactive wastes should be managed in a safe manner to protect human beings and the environment now and in the future. The management strategy depends on collection, segregation, treatment, immobilization, and disposal. The treatment process is a very important step in which the hazardous materials were converted to a more concentrated, less volume and less movable materials. Electrochemistry is the branch of chemistry in which the passage of electric current was producing a chemical change. Electrochemical treatment of radioactive wastes is widely used all over the world. It has a number of advantages and hence benefits. Electrochemistry can lead to remote, automatic control and increasing safety. The present work is focusing on the role of electrochemistry in the treatment of radioactive wastes worldwide. It contains the fundamentals of electrochemistry, the brief story of radioactive wastes, and the modern trends in the electrochemical treatment of radioactive wastes. An overview of electrochemical decomposition of organic wastes, electrochemical reduction of nitrates, electro- precipitation, electro- ion exchange, and electrochemical remediation of soil are outlined. The main operating factors, the mechanism of decontamination, energy consumption and examples of field trials are considered.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  18. Imaging mass spectrometry tackles interfacial challenges in electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xiao-Ying

    2017-12-01

    Electrochemistry has played a significant role in many research fields. Owing to its sensitivity and selectivity, in situ electroanalysis has been widely used as a fast and economical means for achieving outstanding results. Although many spectroscopic techniques have been used in electrochemistry, the challenges to capture short-lived intermediate species as a result of electron transfer in the buried solid electrode and electrolyte solution interface remains a grand challenge. In situ imaging mass spectrometry (IMS) recently has been extended to capture transient species in electrochemistry. This review intends to summarize newest development of IMS and its applications in advancing fundamental electrochemistry.

  19. Catalysis in electrochemistry: from fundamentals to strategies for fuel cell development

    National Research Council Canada - National Science Library

    Santos, Elizabeth; Schmickler, Wolfgang

    2011-01-01

    "Catalysis in Electrochemistry: From Fundamentals to Strategies for Fuel Cell Development is a modern, comprehensive reference work on catalysis in electrochemistry, including principles, methods, strategies, and applications...

  20. Electrochemistry of high-tc superconductors

    International Nuclear Information System (INIS)

    Petrij, O.A.; Tsirlina, G.A.

    1993-01-01

    The review deals with the problems of formation of a new section in modern electrochemistry related to various electrochemical aspects of high-temperature superconductivity. Specific properties of multicomponent oxides as electrode materials are pointed out. The data of experimental works on the study of degradation of superconducting ceramics, electroanalysis of complex oxide systems, electric deposition of metals and polymer films upon them are described. Special attention is paid to electrochemical approaches to electrosynthesis of films, possessing high-temperature superconductivity

  1. Enzymatic Activity Detection via Electrochemistry for Enceladus

    Science.gov (United States)

    Studemeister, Lucy; Koehne, Jessica; Quinn, Richard

    2017-01-01

    Electrochemical detection of biological molecules is a pertinent topic and application in many fields such as medicine, environmental spills, and life detection in space. Proteases, a class of molecules of interest in the search for life, catalyze the hydrolysis of peptides. Trypsin, a specific protease, was chosen to investigate an optimized enzyme detection system using electrochemistry. This study aims at providing the ideal functionalization of an electrode that can reliably detect a signal indicative of an enzymatic reaction from an Enceladus sample.

  2. Condensed matter physics aspects of electrochemistry

    International Nuclear Information System (INIS)

    Tosi, M.P.; Kornyshev, A.A.

    1991-01-01

    This volume collects the proceedings of the Working Party on ''Electrochemistry: Condensed Matter, Atomic and Molecular Physics Aspects'', held for two weeks in the summer of 1990 at the International Centre for Theoretical Physics (ICTP) in Trieste. The goal of the meeting was to discuss those areas of electrochemistry that are accessible to the modern methods of theoretical condensed matter, atomic and molecular physics, in order to stimulate insight and deeper involvement by theoretical physicists into the field. The core of the ICTP Working Party was a set of topically grouped plenary lectures, accompanied by contributed seminars and by the formulation of joint research projects. In the tradition of the ICTP, it was not a meeting of pure theoreticians: about half of the lecturers were professional experimentalists - experts in electrochemistry, physical chemistry, surface science, technical applications. A set of topics was chosen for discussion at the meeting: Liquids, solvation, solutions; The interface (structure, characterization, electric properties, adsorption); Electrodynamics, optics, photo-emission; Charge transfer kinetics (homogeneous and heterogeneous reactions and processes); Superconducting electrodes; Fractal electrodes; Applied research (energy conversion and power sources, electrocatalysis, electroanalysis of turbulent flows). Refs, figs and tabs

  3. Carbon Nanotube Electrodes for Hot-Wire Electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Gründler, P.; Frank, Otakar; Kavan, Ladislav; Dunsch, L.

    2009-01-01

    Roč. 10, č. 3 (2009), s. 559-563 ISSN 1439-4235 R&D Projects: GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : electrochemistry * electrodes * nanotubes * Raman spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 3.453, year: 2009

  4. Application and Utilization of Electrochemistry in Organic Chemistry

    Czech Academy of Sciences Publication Activity Database

    Navrátil, Tomáš

    2011-01-01

    Roč. 15, č. 17 (2011), s. 2921-2922 ISSN 1385-2728 R&D Projects: GA AV ČR IAA400400806 Institutional research plan: CEZ:AV0Z40400503 Keywords : electrochemistry * organic chemistry * applications Subject RIV: CG - Electrochemistry Impact factor: 3.064, year: 2011

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

    Science.gov (United States)

    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…

  6. Electrochemistry of Some New Alkaline Battery Electrodes

    Science.gov (United States)

    1976-02-01

    1NýT;7 ~~ AFAPI 4TR- 75)aI Electrochemistry of Somwý New Alkaline V CI RG, 0OTNME Dr/ David F., ’Pickett, IM Wayue ’,Hisb’q Mr. R ic ha rd A I Mid...adding ZnO to the electi-olyte (saturated) and usi .j the interc:ell conrec;tor d isr:ussed earlier ,itLh el4cc.roploated zinc ag inst. the silver fo

  7. Photothermal deflection spectroscopy investigations of uranium electrochemistry

    International Nuclear Information System (INIS)

    Russo, R.E.; Rudnicki, J.D.

    1993-01-01

    Photothermal Deflection Spectroscopy (PDS) has been successfully applied to the study of uranium oxide electrochemistry. A brief description of PDS and preliminary results that demonstrate the technique are presented. Concentration gradients formed at the electrode surface are measured by this technique. The gradients give insight into the reaction mechanisms. There is some evidence of the initiation of non-electrochemical dissolution of the uranium oxide. Optical absorption by the uranium oxide is measured by PDS and the first results indicate that the absorption of the surface does not change during electrochemical experiments. This result is contrary to literature measurements of bulk samples that indicate that the optical absorption should be strongly changing

  8. NASA Glenn Research Center Electrochemistry Branch Overview

    Science.gov (United States)

    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.

  9. INTERNALIZING ISLAMIC VALUES IN ELECTROCHEMISTRY LEARNING

    Directory of Open Access Journals (Sweden)

    Cucu Zenab Subarkah

    2016-06-01

    Full Text Available The purpose of this paper is to describe a potential way of integrating the knowledge of electrochemistry with a story in the Al-Quran particularly in the sura of Al-Kahfi, verse 83-96. The story tells about an implicit understanding of the concept of electro chemistry. Having the story in the learning of electrochemistry is aimed to internalizing the spirit of Islam in the learning of electro chemistry. Using a classroom action research, this study involved 95 students who are taking the course of Basic Chemistry 2. This study used three instruments, namely: observation sheet of students activity, observation sheet of students attitute, and self-assessment questionnaire. Based on the data, the study found that students were considerably active in each stage of the learning process with the average of activitiy is 78% (good. With regards to attitude, only aspect of responsibility that was not well appeared while the aspects of religious curiosity, cooperative, and communication relatively presented 

  10. Electrochemistry of V2ON with lithium

    International Nuclear Information System (INIS)

    Zhou Yongning; Liu Chang; Chen Huajun; Zhang Long; Li Wenjing; Fu Zhengwen

    2011-01-01

    Highlights: → We have prepared V 2 ON thin film by reactive dc sputtering method and annealing process. → We investigated for its electrochemistry with lithium. → V 2 ON thin films exhibit a large reversible specific capacity of 830 mAh g -1 with much less polarization than VN thin films. → The reversible transformation between nanocrystalline V 2 ON and well dispersed V, Li 2 O, Li 3 N nano-composites were revealed. - Abstract: V 2 ON thin film has been successfully fabricated by reactive dc sputtering method and annealing process and was investigated for its electrochemistry with lithium. The reversible discharge capacities of V 2 ON/Li cells cycled between 0.01 and 4.0 V were found in the range of 803-915 mAh g -1 during the first 50 cycles. By using ex situ scanning electron microscopy, transmission electron microscopy, selected-area electron diffraction and X-ray photoelectron spectroscopy measurements, the reversible transformation between nanocrystalline V 2 ON and well dispersed V, Li 2 O, Li 3 N nano-composites were revealed in the lithium electrochemical reaction. V 2 ON thin film exhibits high reversible capacity and good cycle performance with remarkable lower polarization than VN thin film.

  11. The electrochemistry of IGSCC mitigation

    International Nuclear Information System (INIS)

    Macdonald, D.D.

    2002-01-01

    A brief review is presented of the electrochemical mitigation of intergranular stress corrosion cracking (IGSCC) in watercooled reactor heat transport circuit structural materials. Electrochemical control and mitigation is possible because of the existence of a critical potential for intergranular stress corrosion cracking and due to the feasibility of modifying the environment to displace the corrosion potential to a value that is more negative than the critical value. However, even in cases where the corrosion potential cannot be displaced sufficiently in the negative direction to become more negative than the critical potential, considerable advantage is accrued, because of the roughly exponential dependence of the crack growth rate on potential. The most important parameters in affecting electrochemical control over the corrosion potential and crack growth rate are the kinetic parameters (exchange current densities and Tafel constants) for the redox reactions involving the principal radiolysis products of water (O 2 , H 2 H 2 O 2 ), external solution composition (concentrations of O 2 , H 2 O 2 , and H 2 ), flow velocity, and the conductivity of the bulk environment. The kinetic parameters for the redox reactions essentially determine the charge transfer impedance of the steel surface, which is shown to be one of the key parameters in affecting the magnitude of the coupling current and hence the crack growth rate. The exchange current densities, in particular, are amenable to control by catalysis or inhibition, with the result that surface modification techniques are highly effective in controlling and mitigating intergranular stress corrosion cracking in reactor coolant circuit materials. (orig.)

  12. Applications of ultrasound in electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Silva Martinez, Susana

    1997-10-01

    The effect of the ultrasound on electrochemical processes has been investigated employing a microelectrode within the cavitating media. Transient mass transport was strongly enhanced in the presence of ultrasound. High rates of mass transfer of up to 1.5 cm s-1 were observed. These high rates of mass transfer were attributed to two cavitation processes. First, bubble collapse at or near the solid-liquid interface with the consequent formation of a high speed liquid microjet directed at the electrode surface. Second, bubble motion near or within the diffusion layer or the electrode. Single current transients were also recorded at high time resolution. These single current transients were attributed to the short-time perturbation of the diffusion field of the microelectrode due to impacts of cavitation bubble collapse followed by a long time relaxation of the diffusion field back to the steady state. The influence of the ultrasonic source to electrode separation, temperature of the bulk solution, electrode potential and electrode size on the magnitude of current transients was also studied. All of these parameters affected markedly the magnitude of the current transients recorded at microelectrode in the presence of ultrasound. An alternative approach is presented to characterise fast heterogeneous electron transfer reactions employing ultrasound as a mass transport enhancement tool. Two innovative techniques, sampled-current voltammetry and sampled-mean current voltammetry, were developed during the course of this thesis. The technique of sample-current voltammetry reported values of the standard rate constant of heterogeneous electron transfer of up to 1.2 cm s-1 in the presence of ultrasound. This technique focuses on the electrochemical phenomena under investigation at the point of impact of the ultrasonic event, produced by asymmetric cavitation bubble collapse near the electrode surface. Bubble dynamics were also examined under the experimental conditions

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

    Science.gov (United States)

    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.

  14. Annals of the 4. Brazilian Symposium on Electrochemistry and Electroanalytics

    International Nuclear Information System (INIS)

    1984-01-01

    Theoretical and experimental papers on electrochemistry and electroanalysis are presented. The techniques used are: voltametry, polarography, ellipsometry, coulometric titration, luminescence, potentiometry, electrodeposition and photoelectrochemistry. (C.L.B.) [pt

  15. Electrochemistry-based Battery Modeling for Prognostics

    Science.gov (United States)

    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.

  16. 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.

    Science.gov (United States)

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Electrochemistry and Spectroelectrochemistry of Bioactive Hydroxyquinolines: A Mechanistic Study

    Czech Academy of Sciences Publication Activity Database

    Sokolová, Romana; Nycz, J. E.; Ramešová, Šárka; Fiedler, Jan; Degano, I.; Szala, M.; Kolivoška, Viliam; Gál, M.

    2015-01-01

    Roč. 119, č. 20 (2015), s. 6074-6080 ISSN 1520-6106 Grant - others:Rada Programu interní podpory projektů mezinárodní spolupráce AV ČR M200401201 Program:M Institutional support: RVO:61388955 Keywords : electrochemistry * spectroelectrochemistry * Bioactive Hydroxyquinolines Subject RIV: CG - Electrochemistry Impact factor: 3.187, year: 2015

  18. Proceedings of the ISEAC international symposium cum workshop on electrochemistry

    International Nuclear Information System (INIS)

    Aggarwal, Suresh K.; Guin, Saurav K.; Kamat, Jayshree V.; Gupta, Ruma

    2011-01-01

    This symposium highlights the role of chemistry to find out the solution of some global problems. Among the leading branches of chemistry, the foot prints of electrochemistry can be seen in a variety of fields for both fundamental studies and methodological applications. Electrochemistry and allied science has already exhibited its potential to meet the world's need starting from health and medicine, environment, nanofabrication to alternate energy resources. Articles relevant to INIS are indexed separately

  19. A novel biosensor based on the direct electrochemistry of horseradish peroxidase immobilized in the three-dimensional flower-like Bi{sub 2}WO{sub 6} microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hui, E-mail: liuhui@sust.edu.cn; Guo, Kai; Duan, Congyue; Chen, Xianjin; Zhu, Zhenfeng

    2016-07-01

    Three-dimensional flower-like Bi{sub 2}WO{sub 6} microspheres (3D-Bi{sub 2}WO{sub 6} MSs) have been synthesized through a simple hydrothermal method. The morphology and structure of 3D-Bi{sub 2}WO{sub 6} MSs were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The 3D-Bi{sub 2}WO{sub 6} MSs subsequently were used to immobilize horseradish peroxidase (HRP) and fabricate a mediator-free biosensor for the detection of H{sub 2}O{sub 2}. Spectroscopic and electrochemical results reveal that 3D-Bi{sub 2}WO{sub 6} MSs constitute an excellent immobilization matrix with biocompatibility for enzymes. Meanwhile, due to unique morphology of the flower-like microspheres, the direct electron transfer of HRP is facilitated and the prepared biosensors display good performances for the detection of H{sub 2}O{sub 2} with a wide linear range, including two linear sections: 0.5–100 μM (R{sup 2} = 0.9983) and 100–250 μM (R{sup 2} = 0.9981), as well as an extremely low method detection limit of 0.18 μM. - Highlights: • 3D-Bi{sub 2}WO{sub 6} microspheres are used to fabricate a mediator-free biosensor firstly. • The biosensor displays a wide linear range of 0.5–250 μM for H{sub 2}O{sub 2}. • The biosensor exhibits a low detection limit of 0.18 μM for H{sub 2}O{sub 2}.

  20. Sonochemical synthesis of magnetic core-shell Fe{sub 3}O{sub 4}-ZrO{sub 2} nanoparticles and their application to the highly effective immobilization of myoglobin for direct electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Peng Huaping; Liang Ruping; Zhang Li [Department of Chemistry, Nanchang University, Nanchang 330031 (China); Qiu Jianding, E-mail: jdqiu@ncu.edu.c [Department of Chemistry, Nanchang University, Nanchang 330031 (China)

    2011-04-15

    Graphical abstract: Display Omitted Highlights: Magnetic core-shell Fe{sub 3}O{sub 4}-ZrO{sub 2} nanoparticle was synthesized by sonochemical approach. Fe{sub 3}O{sub 4}-ZrO{sub 2} NPs provided high capacity for trapping Mb on magnetic glassy carbon electrode surface. The constructed Mb/Fe{sub 3}O{sub 4}-ZrO{sub 2} film exhibited excellent electrocatalytic ability for the reduction of H{sub 2}O{sub 2}. The proposed method simplifies the immobilization methodology of proteins. - Abstract: In this study, bifunctional Fe{sub 3}O{sub 4}-ZrO{sub 2} magnetic core-shell nanoparticles (NPs), synthesized by a simple and effective sonochemical approach, were attached to the surface of a magnetic glassy carbon electrode (MGCE) and successfully applied to the immobilization/adsorption of myoglobin (Mb) for constructing a novel biosensor platform. With the advantages of the magnetism and the excellent biocompatibility of the Fe{sub 3}O{sub 4}-ZrO{sub 2} NPs, Mb could be easily immobilized on the surface of the electrode in the present of external magnetic field and well retained its bioactivity, hence dramatically facilitated direct electron transfer of Mb was demonstrated. The proposed Mb/Fe{sub 3}O{sub 4}-ZrO{sub 2} biofilm electrode exhibited excellent electrocatalytic behaviors towards the reduction of H{sub 2}O{sub 2} with a linear range from 0.64 {mu}M to 148 {mu}M. This presented system avoids the complex synthesis for protecting Fe{sub 3}O{sub 4} NPs, supplies a simple, effective and inexpensive way to immobilize protein, and is promising for construction of third-generation biosensors and other bio-magnetic induction devices.

  1. Criticality studies; Etudes de criticite

    Energy Technology Data Exchange (ETDEWEB)

    Breton, D; Lecorche, P; Clouet d' Orval, Ch [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-07-01

    Criticality studies made at the Commissariat a l'Energie atomique deal on the one hand with experiments on plutonium and uranium solutions, on the other hand with theoretical work on the development and use of computation, methods for the resolution of problems concerning the nuclear safety of chemical and metallurgical plants. I - Since 1958 the experimental studies have dealt with homogeneous media constituted by a fissile salt dissolved in light water. Developed using the reactor Proserpine, the experiments have been carried on at Saclay on the Alecto assemblies where solutions of plutonium or of 90 p.100 - enriched uranium can be made critical. The results already obtained relate to critical masses of cylindrical tanks of diameters from 20 to 50 cm. reflected in several ways (water, concrete, etc. . ) at concentrations up to 100 g/liter. Physical measurements (spectra, reactor noises) and interaction measurements complete the results. Other experiments relating to plutonium solutions were begun in 1963, at the Valduc Center. They deal with the study of critical masses of annular vessels of external diameter 50 cm and internal diameter varying from 10 to 30 cm. These vessels can be water reflected internally, externally, or both. Two of these vessels have been studied in interaction for various geometries. Slabs of various thicknesses were also studied. II - The studies thus undertaken allowed the development of methods of computation which have been tested on several experiments. Particular use has been made of the possibilities of calculations based on transport theory and on Monte Carlo methods. All these theoretical studies are applied to the design and control of industrial plants from the point of view of safety. (authors) [French] Les etudes de criticite effectuees au CEA comportent d'une part des experiences sur des solutions de plutonium et d'uranium enrichi, d'autre part des travaux theoriques portant sur la mise au point et l'exploitation de methodes

  2. Contribution to the study of the behaviour of solid particles in a confined turbulent flow using direct numerical simulation; Contribution a l'etude du comportement de particules solides en ecoulement turbulent confine par simulation numerique directe

    Energy Technology Data Exchange (ETDEWEB)

    Rambaud, P.

    2001-11-01

    The theme of this numerical thesis is on the behavior of solid particles embedded in a non-homogeneous and non-isotropic turbulent gas flow as the one tacking place in a plane channel. The turbulence is generated through the direct numerical simulation of Navier-Stokes equations discretized by formally second order in time and space finite difference operators. This Eulerian vision of the incompressible gas flow is completed by a Lagrangian formulation allowing to follow solid particles. In this formulation, the considered forces are the non-linear drag and the Saffman lift both corrected for wall effects. Furthermore, depending on the test cases studied, particle bouncing forces on the wall, gravity or electrostatic forces are taken into account. A three-dimensional Hermitian interpolation highlight the special care spend on the determination of the fluid velocity at the solid particle location. The first code application is dedicated to solid particles dispersion inside an horizontal channel, or in a channel operated in a weightlessness state. The huge amount of data from the Lagrangian tracking is reduced to the integral times of the turbulence seen by the solid particles on their trajectories. Those times are crucial in Lagrangian methods associated with a low numerical cost compared with the ones used in the present study. Among those methods, the one based on Langevin type equations have the best potential to handle industrial type problems. Nevertheless, this method needs to rebuild the fluid velocity fluctuations seen by the solid particles on their trajectories. This technic is able to reproduce the crossing trajectory effect, the inertial effect and the continuity effect, only if the integral times of the turbulence seen are known. Till now, those times were known thanks to a semi-empirical correlation from direct numerical simulation in homogeneous and isotropic turbulence (Wang and Stock 1993). However, although these conditions, this correlation was

  3. Asymptotic analysis, direct numerical simulation and modeling of premixed turbulent flame-wall interaction; Etude asymptotique, simulation numerique directe et modelisation de l`interaction flamme turbulente premelangee-paroi

    Energy Technology Data Exchange (ETDEWEB)

    Bruneaux, G.

    1996-05-20

    Premixed turbulent flame-wall interaction is studied using theoretical and numerical analysis. Laminar interactions are first investigated through a literature review. This gives a characterization of the different configurations of interaction and justifies the use of simplified kinetic schemes to study the interaction. Calculations are then performed using Direct Numerical Simulation with a one-step chemistry model, and are compared with good agreements to asymptotic analysis. Flame-wall distances and wall heat fluxes obtained are compared successfully with those of the literature. Heat losses decrease the consumption rate, leading to extinction at the maximum of wall heat flux. It is followed by a flame retreat, when the fuel diffuses into the reaction zone, resulting in low unburnt hydrocarbon levels. Then, turbulent regime is investigated, using two types of Direct Numerical Simulations: 2D variable density and 3D constant density. Similar results are obtained: the local turbulent flame behavior is identical to a laminar interaction, and tongues of fresh gases are expelled from the wall region, near zones of quenching. In the 2D simulations, minimal flame-wall distances and maximum wall heat fluxes are similar to laminar values. However, the structure of the turbulence in the 3D calculations induces smaller flame-wall distances and higher wall heat fluxes. Finally, a flame-wall interaction model is built and validated. It uses the flamelet approach, where the flame is described in terms of consumption speed and flame surface density. This model is simplified to produce a law of the wall, which is then included in a averaged CFD code (Kiva2-MB). It is validated in an engine calculation. (author) 36 refs.

  4. Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media

    Czech Academy of Sciences Publication Activity Database

    Staszak-Jirkovský, J.; Subbaraman, R.; Strmcnik, D.; Harrison, K. L.; Diesendruck, Ch. E.; Assary, R.; Frank, Otakar; Kobr, L.; Wiberg, G. K. H.; Genorio, B.; Connell, J. G.; Lopes, P. P.; Stamenkovic, V. R.; Curtiss, L.; Moore, J. S.; Zavadil, K. R.; Markovic, N. M.

    2015-01-01

    Roč. 5, č. 11 (2015), s. 6600-6607 ISSN 2155-5435 Institutional support: RVO:61388955 Keywords : electrochemistry * electrocatalysis * binding energy Subject RIV: CG - Electrochemistry Impact factor: 9.307, year: 2015

  5. Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum; Etude de l`oxydation electrochimique directe et indirecte de l`hydrazine en milieu acide nitrique sur platine

    Energy Technology Data Exchange (ETDEWEB)

    Cames, B

    1997-12-31

    allow consideration of the process of direct electrochemical oxidation of hydrazine to nitrogen, and of Pu(III) to Pu(IV), with electrochemical yields of 100 %. (author) 59 refs.

  6. Sulfur ligand mediated electrochemistry of gold surfaces and nanoparticles: what, how, and why

    DEFF Research Database (Denmark)

    Chi, Qijin; Ford, Michael J.; Halder, Arnab

    2017-01-01

    Gold surfaces are widely used in electrochemistry whilst gold nanoparticles have very many uses, with both the surfaces and the particles often being protected by sulfur-bound organic ligands. The ligands not only provide chemical stability but also directly participate in many desired processes....... This review considers the diversity of known atomic structures for gold-sulfur interfaces, how these structures facilitate a diversity of mechanisms in electrochemical applications, and why this is possible based on recent advances in the basic understanding of the electronic structure of gold-sulfur bonds...

  7. Environmental aspects of electrochemistry and photoelectrochemistry

    International Nuclear Information System (INIS)

    Tomkiewicz, M.; Yoneyama, H.; Hori, Y.

    1993-01-01

    Arguably, the end of this century marks the beginning of an era in which an equilibrium between men and environment is no longer an option but a necessity. A full life cycle of new and old technologies will soon be a requirement. Electrochemistry probably plays a more fundamental role toward the end of the life-cycle of many technologies as compared to the beginning of the cycle. This symposium is the first of its kind within the Electrochemical Society in its attempt to unify diverse aspects of the environmental picture. In addition to the scientific interest in the various topics, this diversity reflects the various priorities that emerge in different countries. In Japan a strong emphasis is being put on the environmental consequences of CO 2 accumulation and hence the strong emphasis on CO 2 fixation. In the US and Europe the detoxification of aquatic environments seems at present to attract higher priorities. Almost everywhere there is a need to remedy the cumulative effect of total neglect since the dawn of the industrial revolution that can be traced differently in different parts of the world. In a somewhat arbitrary way the authors have divided the contributions into three categories: (1) CO 2 fixation, (2) Photocatalysis with TiO 2 , (3) Electrochemical decontaminations. Although this partition was done mainly for editorial convenience, it follows closely the clustering at the meeting. Individual papers are cataloged separately for inclusion in the appropriate data bases

  8. Electrochemistry of plutonium in molten halides

    International Nuclear Information System (INIS)

    McCurry, L.E.; Moy, G.M.M.; Bowersox, D.F.

    1987-01-01

    The electrochemistry of plutonium in molten halides is of technological importance as a method of purification of plutonium. Previous authors have reported that plutonium can be purified by electrorefining impure plutonium in various molten haldies. Work to eluciate the mechanism of the plutonium reduction in molten halides has been limited to a chronopotentiometric study in LiCl-KCl. Potentiometric studies have been carried out to determine the standard reduction potential for the plutonium (III) couple in various molten alkali metal halides. Initial cyclic voltammetric experiments were performed in molten KCL at 1100 K. A silver/silver chloride (10 mole %) in equimolar NaCl-KCl was used as a reference electrode. Working and counter electrodes were tungsten. The cell components and melt were contained in a quartz crucible. Background cyclic voltammograms of the KCl melt at the tungsten electrode showed no evidence of electroactive impurities in the melt. Plutonium was added to the melt as PuCl/sub 3/, which was prepared by chlorination of the oxide. At low concentrations of PuCl/sub 3/ in the melt (0.01-0.03 molar), no reduction wave due to the reduction of Pu(III) was observed in the voltammograms up to the potassium reduction limit of the melt. However on scan reversal after scanning into the potassium reduction limit a new oxidation wave was observed

  9. Molybdenum, molybdenum oxides, and their electrochemistry.

    Science.gov (United States)

    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.

  10. Developments in electrochemistry science inspired by Martin Fleischmann

    CERN Document Server

    Pletcher, Derek; Williams, David

    2014-01-01

    Martin Fleischmann was truly one of the 'fathers' of modern electrochemistry having made major contributions to diverse topics within electrochemical science and technology. These include the theory and practice of voltammetry and in situ spectroscopic techniques, instrumentation, electrochemical phase formation, corrosion, electrochemical engineering, electrosynthesis and cold fusion.  While intended to honour the memory of Martin Fleischmann, Developments in Electrochemistry is neither a biography nor a history of his contributions. Rather, the book is a series of critical reviews of topic

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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. © 2011 Bentham Science Publishers Ltd.

  13. ETUDE - European Trade Union Distance Education.

    Science.gov (United States)

    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…

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  15. Synthesis, spectra and electrochemistry of dinitro-bis- {2-(phenylazo ...

    Indian Academy of Sciences (India)

    Unknown

    2006-09-18

    Sep 18, 2006 ... Synthesis, spectra and electrochemistry of dinitro-bis-. {2-(phenylazo)pyrimidine} ruthenium(II). Nitro–nitroso derivatives and reactivity of the electrophilic nitrosyl centre. PRITHWIRAJ BYABARTTA. Department of Chemistry, The University of Burdwan, Burdwan 713 104. Present address: Departmento de ...

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

    Science.gov (United States)

    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…

  17. Introduction to Electrochemistry and the Use of Electrochemistry to Synthesize and Evaluate Catalysts for Water Oxidation and Reduction

    Science.gov (United States)

    Hendel, Samuel J.; Young, Elizabeth R.

    2016-01-01

    Electrochemical analysis is an important skill to teach in chemistry curricula because it is a critical tool in current high-impact chemical research. Electrochemistry enables researchers to analyze a variety of systems extending from molecules to materials that encompass research themes ranging from clean energy to substrate activation in…

  18. 2D Cross Sectional Analysis and Associated Electrochemistry of Composite Electrodes Containing Dispersed Agglomerates of Nanocrystalline Magnetite, Fe₃O₄.

    Science.gov (United States)

    Bock, David C; Kirshenbaum, Kevin C; Wang, Jiajun; Zhang, Wei; Wang, Feng; Wang, Jun; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

    2015-06-24

    When electroactive nanomaterials are fully incorporated into an electrode structure, characterization of the crystallite sizes, agglomerate sizes, and dispersion of the electroactive materials can lend insight into the complex electrochemistry associated with composite electrodes. In this study, composite magnetite electrodes were sectioned using ultramicrotome techniques, which facilitated the direct observation of crystallites and agglomerates of magnetite (Fe3O4) as well as their dispersal patterns in large representative sections of electrode, via 2D cross sectional analysis by Transmission Electron Microscopy (TEM). Further, the electrochemistry of these electrodes were recorded, and Transmission X-ray Microscopy (TXM) was used to determine the distribution of oxidation states of the reduced magnetite. Unexpectedly, while two crystallite sizes of magnetite were employed in the production of the composite electrodes, the magnetite agglomerate sizes and degrees of dispersion in the two composite electrodes were similar to each other. This observation illustrates the necessity for careful characterization of composite electrodes, in order to understand the effects of crystallite size, agglomerate size, and level of dispersion on electrochemistry.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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).

  1. Nouvelles: KEK: B pour BELLE; NA48 mesure la violation directe de CP; LEL: le laser à électrons libres dépasse le kilowatt; Le LEP à 100 pour 100; Tour d'honneur au RHIC; Mesures de précision; Etude sur les modes de gestion du village planétaire; Conférence PANIC99 à Uppsala; Rencontre électron-noyau à HERA; LPP, Doubna célèbre une décennie; Les physiciens auscultent le photon; Aimants chauds venus du froid

    CERN Multimedia

    1999-01-01

    Nouvelles: KEK: B pour BELLE; NA48 mesure la violation directe de CP; LEL: le laser à électrons libres dépasse le kilowatt; Le LEP à 100 pour 100; Tour d'honneur au RHIC; Mesures de précision; Etude sur les modes de gestion du village planétaire; Conférence PANIC99 à Uppsala; Rencontre électron-noyau à HERA; LPP, Doubna célèbre une décennie; Les physiciens auscultent le photon; Aimants chauds venus du froid

  2. Fundamentals and applications of organic electrochemistry synthesis, materials, devices

    CERN Document Server

    Fuchigami, Toshio; Inagi, Shinsuke

    2014-01-01

    This textbook is an accessible overview of the broad field of organic electrochemistry, covering the fundamentals and applications of contemporary organic electrochemistry.  The book begins with an introduction to the fundamental aspects of electrode electron transfer and methods for the electrochemical measurement of organic molecules. It then goes on to discuss organic electrosynthesis of molecules and macromolecules, including detailed experimental information for the electrochemical synthesis of organic compounds and conducting polymers. Later chapters highlight new methodology for organic electrochemical synthesis, for example electrolysis in ionic liquids, the application to organic electronic devices such as solar cells and LEDs, and examples of commercialized organic electrode processes. Appendices present useful supplementary information including experimental examples of organic electrosynthesis, and tables of physical data (redox potentials of various organic solvents and organic compounds and phy...

  3. Advances in molten salt electrochemistry towards future energy systems

    International Nuclear Information System (INIS)

    Ito, Yasuhiko

    2005-01-01

    This review article describes some selected novel molten salt electrochemical processes which have been created/developed by the author and his coworkers, with emphasis on the applications towards future energy systems. After showing a perspective of the applications of molten salt electrochemistry from the viewpoints of energy and environment, several selected topics are described in detail, which include nitride fuel cycle in a nuclear field, hydrogen energy system coupled with ammonia economy, thermally regenerative fuel cell systems, novel Si production process for solar cell and novel molten salt electrochemical processes for various energy and environment related functional materials including nitrides, rare earth-transition metal alloys, fine particles obtained by plasma-induced electrolysis, and carbon film. And finally, the author stresses again, the importance and potential of molten salt electrochemistry, and encourages young students, scientists and researchers to march in a procession hand in hand towards a bright future of molten salts. (author)

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

    Science.gov (United States)

    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

  5. The bioinorganic electrochemistry of vanadium-penicillamine complexes

    International Nuclear Information System (INIS)

    Bagal, U.A.; Riechel, T.L.

    1989-01-01

    Vanadium (V) has been found to inhibit (Na + , K + )-ATPase in the sodium pump reaction in erythrocytes. Glutathione has been suggested as the reducing agent that reverses the effect by reducing vanadium to the (IV) oxidation state. Penicillamine is being studied as a model for glutathione since both have sulfhydryl groups which are involved in redox and coordination chemistry. The electrochemistry in DMSO of penicillamine, its carboxylic ester, and their VO 2 + complexes are discussed in this paper

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  8. 2010 Gordon Research Conference, Electrochemistry, January 9-15, 2010

    Energy Technology Data Exchange (ETDEWEB)

    Creager, Stephen [Clemson Univ., SC (United States)

    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.

  9. Non-haloaluminate room-temperature ionic liquids in electrochemistry--a review.

    Science.gov (United States)

    Buzzeo, Marisa C; Evans, Russell G; Compton, Richard G

    2004-08-20

    Some twenty-five years after they first came to prominence as alternative electrochemical solvents, room temperature ionic liquids (RTILs) are currently being employed across an increasingly wide range of chemical fields. This review examines the current state of ionic liquid-based electrochemistry, with particular focus on the work of the last decade. Being composed entirely of ions and possesing wide electrochemical windows (often in excess of 5 volts), it is not difficult to see why these compounds are seen by electrochemists as attractive potential solvents. Accordingly, an examination of the pertinent properties of ionic liquids is presented, followed by an assessment of their application to date across the various electrochemical disciplines, concluding with an outlook viewing current problems and directions.

  10. Etude de la violation de $CP$ directe pour l'extraction de l'angle $\\gamma$ via le canal de désintégration $B^{\\pm} \\rightarrow \\pi^{\\pm} \\pi^{\\mp} K^{\\pm}$. Etude d'un algorithme d'identification de particules dans le RICH 2 de LHCb

    CERN Document Server

    Gilles, G

    2007-01-01

    LHCb est une expérience consacrée à la physique des hadrons {it beaux} dont les premières prises de données sont prévues vers $2008$.\\ Le but de l'expérience {it LHCb} est l'étude précise de la violation de {it CP} dans le secteur de la {it beauté}. Ces particules seront produites dans les collisions proton-proton, qui auront lieu dans le futur collisionneur hadronique LHC du CERN près de Genève. La grande précision de l'expérience et la statistique disponible ($10^{12}$ événements {it beaux} par an) permettront de contraindre fortement le modèle standard et de tester sa validité. \\ L'étude de la {it violation directe de CP} dans le canal des mésons {it beaux} chargés est très prometteuse mais délicate tant les probabilités de désintégrations de ces derniers, dans les canaux susceptibles de violer la symétrie {it CP}, sont faibles ($sim 10^{-5}$). D'autre part, l'effet de {it violation de CP directe} attendu est très faible.\\ Afin de "concentrer" l'effet de {it violation de CP}, l'...

  11. Dinuclear ruthenium sawhorse-type complexes containing carboxylato bridges and ferrocenyl substituents: Synthesis and electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Auzias, M.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

    2007-01-01

    Roč. 360, č. 6 (2007), s. 2023-2028 ISSN 0020-1693 Institutional research plan: CEZ:AV0Z40400503 Keywords : carboxylato bridges * dinuclear complexes * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 1.713, year: 2007

  12. Discussion meet on role of electrochemistry in biosensors, nano-materials, fuel cells and ionic liquids

    International Nuclear Information System (INIS)

    Aggarwal, S.K.; Gopinath, N.; Sharma, M.K.

    2006-09-01

    Electrochemistry is a challenging as well as fascinating branch of chemistry, which is finding applications in almost all areas of science and technology. This present discussion covers invited talks and contributed papers on electrochemical biomimetic sensing, electrochemical immuno sensing, electrochemistry of nano-particles and electrowinning. Papers relevant to INIS are indexed separately

  13. Proceedings of the fifth ISEAC triennial international conference on advances and recent trends in electrochemistry

    International Nuclear Information System (INIS)

    Aggarwal, Suresh K.; Guin, Saurav K.; Sharma, Manoj K.; Kamat, Jayshree V.; Ambolikar, Arvind S.

    2013-01-01

    The fifth international conference on advances and recent trends in electrochemistry was held during January 16-20, 2013 at Hyderabad. The topics covered under it were on electrochemistry and different branches of science and technology including nuclear science. Articles on electrochemical quartz crystal microbalance, scanning electrochemical microscope, electrochemical biosensors and ionic liquids are also included. Papers relevant to INIS are indexed separately

  14. The importance of V.G. Levich’s research in the development of modern electrochemistry

    DEFF Research Database (Denmark)

    Ulstrup, J.; Vorotyntsev, M. A.; Davydov, A. D.

    2017-01-01

    The fundamental scientific areas founded and developed by V.G. Levich and his school, and their importance in contemporary theoretical electrochemistry have been overviewed.......The fundamental scientific areas founded and developed by V.G. Levich and his school, and their importance in contemporary theoretical electrochemistry have been overviewed....

  15. Instrumental performance of an etude after three methods of practice.

    Science.gov (United States)

    Vanden Ark, S

    1997-12-01

    For 80 fifth-grade students three practice conditions (mental, mental with physical simulation, and physical with singing) produced significant mean differences in instrumental performance of an etude. No significant differences were found for traditional, physical practice.

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

    Directory of Open Access Journals (Sweden)

    Sanju Gupta

    2017-09-01

    Full Text Available 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

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

    Science.gov (United States)

    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 membrane separated

  18. Low temperature electrochemistry at normal conductor/frozen electrolyte interface

    International Nuclear Information System (INIS)

    Borkowska, Z.; Stimming, U.

    1991-01-01

    The frozen electrolyte technique (FREECE = FRozen Electrolyte ElectroChEmistry) is based on the experimental result that frozen electrolytes are suitable for electrochemical studies. This technique has been used in our laboratory and also by others to investigate interfacial electrochemical behavior. An argument will be given as to why the FREECE technique is advantageous in a number of respects and what kind of electrolyte systems can be used. Reference is made to electrochemical results such as interfacial reactions and double layer properties. 26 refs

  19. Nanoscale methods for single-molecule electrochemistry.

    Science.gov (United States)

    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.

  20. Electroanalytical Evaluation of Nanoparticles by Nano-impact Electrochemistry

    Science.gov (United States)

    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

  1. Electrochemical oxidation of quaternary ammonium electrolytes : Unexpected side reactions in organic electrochemistry

    NARCIS (Netherlands)

    Nouri Nigjeh, Eslam; de Vries, Marcel; Bruins, Andries P.; Bischoff, Rainer; Permentier, Hjalmar P.

    Quaternary ammonium salts are among the most widely used electrolytes in organic electrochemistry, but there is little known about their unwanted side oxidation reactions. We have, therefore, studied the constant potential oxidation products of quaternary ammonium electrolytes using mass

  2. Electro-Fermentation - Merging Electrochemistry with Fermentation in Industrial Applications.

    Science.gov (United States)

    Schievano, Andrea; Pepé Sciarria, Tommy; Vanbroekhoven, Karolien; De Wever, Heleen; Puig, Sebastià; Andersen, Stephen J; Rabaey, Korneel; Pant, Deepak

    2016-11-01

    Electro-fermentation (EF) merges traditional industrial fermentation with electrochemistry. An imposed electrical field influences the fermentation environment and microbial metabolism in either a reductive or oxidative manner. The benefit of this approach is to produce target biochemicals with improved selectivity, increase carbon efficiency, limit the use of additives for redox balance or pH control, enhance microbial growth, or in some cases enhance product recovery. We discuss the principles of electrically driven fermentations and how EF can be used to steer both pure culture and microbiota-based fermentations. An overview is given on which advantages EF may bring to both existing and innovative industrial fermentation processes, and which doors might be opened in waste biomass utilization towards added-value biorefineries. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Common Principles of Molecular Electronics and Nanoscale Electrochemistry.

    Science.gov (United States)

    Bueno, Paulo Roberto

    2018-05-24

    The merging of nanoscale electronics and electrochemistry can potentially modernize the way electronic devices are currently engineered or constructed. It is well known that the greatest challenges will involve not only miniaturizing and improving the performance of mobile devices, but also manufacturing reliable electrical vehicles, and engineering more efficient solar panels and energy storage systems. These are just a few examples of how technological innovation is dependent on both electrochemical and electronic elements. This paper offers a conceptual discussion of this central topic, with particular focus on the impact that uniting physical and chemical concepts at a nanoscale could have on the future development of electroanalytical devices. The specific example to which this article refers pertains to molecular diagnostics, i.e., devices that employ physical and electrochemical concepts to diagnose diseases.

  4. Comparative electrochemistry of technetium (V) and rhenium (V) dioxo complexes

    International Nuclear Information System (INIS)

    Kremer, C.; Kremer, E.; Dominguez, S.; Mederos, A.

    1996-01-01

    The heavy use of 99m Tc in nuclear medicine and the recent development of 188 Re radiopharmaceuticals have encouraged the comparative study of Tc and Re coordination compounds. In this work, the electrochemistry of [M v O 2 (amine) 2 ] + (M = Tc, Re; amine = ethylenediamine, 1,3-diaminopropane, diethylenetriamine, triethylenetetramine) complexes is studied by cyclic voltammetry and the results are compared. The voltammograms of these compounds, obtained at different pH values, show that [ReO 2 (amine) 2 + cations are thermodynamically stable even when protonated. On the other hand, analogous Tc compounds are not so stable and easily decompose if existing as [TcO (OH) (amine) 2 ] 2+ . (author). 17 refs., 3 figs., 1 tab

  5. A compact double crystal monochromator for electrochemistry beamline at PLS

    CERN Document Server

    Rah, S; Kim, G H

    2001-01-01

    A compact double crystal monochromator based on 16.5'' CF flange has been designed, fabricated and installed for electrochemistry beamline at Pohang light source. The Bragg angle range of the monochromator is 7-75 deg. The mechanical design is modified from typical Boomerang design [J.A. Golovchenko et al., Rev. Sci. Instrum. 52 (1981) 509; J.P. Kirkland, Nucl. Instr. and Meth. A291 (1990) 185] to have fixed beam offset and single driving axis for spectroscopy experiments. The parallelism error of the crystals is minimized to less than 6 mu rad for the range, by using a precision single axis linear guide, Also, the number of mechanical parts in the vacuum is minimized and 1.8x10 sup - sup 9 Torr of vacuum is achieved without baking.

  6. Plastic reactor suitable for high pressure and supercritical fluid electrochemistry

    DEFF Research Database (Denmark)

    Branch, Jack; Alibouri, Mehrdad; Cook, David A.

    2017-01-01

    The paper describes a reactor suitable for high pressure, particularly supercritical fluid, electrochemistry and electrodeposition at pressures up to 30 MPa at 115◦C. The reactor incorporates two key, new design concepts; a plastic reactor vessel and the use of o-ring sealed brittle electrodes...... by the deposition of Bi. The application of the reactor to the production of nanostructures is demonstrated by the electrodeposition of ∼80 nm diameter Te nanowires into an anodic alumina on silicon template. Key advantages of the new reactor design include reduction of the number of wetted materials, particularly...... glues used for insulating electrodes, compatability with reagents incompatible with steel, compatability with microfabricated planar multiple electrodes, small volume which brings safety advantages and reduced reagent useage, and a significant reduction in experimental time....

  7. Selenium electrochemistry. Applications in the nuclear fuel cycle

    Energy Technology Data Exchange (ETDEWEB)

    Maslennikov, A.; Peretroukhine, V. [Russian Academy of Sciences, Moscow (Russian Federation). Inst. of Physical Chemistry; David, F. [Centre National de la Recherche Scientifique (CNRS), 91 - Orsay (France); Lecomte, M. [CEA Centre d' Etudes de la Valle du Rhone, 30 - Marcoule (France). Direction du Cycle du Combustible

    1999-07-01

    Modern state of selenium electrochemistry is reviewed in respect of the application of electrochemical methods for the study of the behavior of this element and its quantitative analysis in the solutions of nuclear fuel cycle. The review includes the data on the redox potentials of Se in aqueous solutions, and the data on Se redox reactions, occurring at mercury and solid electrodes. Analysis of the available literature data shows that the inverse stripping voltammetry technique for trace Se concentration and determination seems to be the most promising in application for the Se determination in PUREX solutions and in radioactive wastes. The adaptation of the ISV technique for the trace Se concentration and determination in the solutions of the nuclear fuel cycle is indicated as the most prospective goal of the future experimental study. (author)

  8. Electrochemistry of conjugated planar anticancer molecules: Irinotecan and Sunitinib

    International Nuclear Information System (INIS)

    Zotti, Gianni; Berlin, Anna; Vercelli, Barbara

    2017-01-01

    The evaluation of drug levels is important for personalized therapeutic approaches particularly in cancer care. To this end electrochemistry provides simplicity, low cost, high sensitivity and possibility of miniaturization. Here we report the electrochemistry and UV-visible spectroscopy of two extensively used planar conjugated anticancer molecules, Irinotecan (ITC) and Sunitinib (SUN), in aprotic medium and water. Comparison is made with model compounds without amine ends. The electronic spectra of ITC and SUN in dimethylsulfoxide show similar vibronic patterns (0.2 eV vibrational energy for both) with energy gaps of 3.1 and 2.5 eV respectively. Cyclic voltammetry in acetonitrile shows the same one-electron reduction peak (-1.9 V vs Ag/Ag + ) and oxidation peaks at 1.45 and 0.65 V, both beyond the oxidation of the amine ends (0.45 V). In water the optical energy gaps are unchanged but the vibronic structure is almost lost and the oxidation processes are eased by 0.45 V for SUN and 1.10 V for ITC. The number of oxidatively exchanged electrons in water is two for ITC but four in two subsequent two-electron steps for SUN. The overall oxidation process for ITC likely involves the nucleophilic attack of a water molecule to the quinoline moiety. The first two-electron oxidation of SUN, involving the pyrrole moiety, leads possibly to the conjugated imine ring which is further oxidized to the N-oxide form. Lowering of the electron-transfer activation energy by water is assigned in part to release of molecular rigidity but in ITC the major role is assigned to a nucleophilic attack of water already in the activated state.

  9. Nanomaterials based on carbon and Ti(IV) oxides: some aspects of their electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav

    2012-01-01

    Roč. 9, 8/9 (2012), s. 652-679 ISSN 1475-7435 R&D Projects: GA MŠk LC510; GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : carbon nanostructures * titanium oxide * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 1.087, year: 2012

  10. Covalent Dimers of 1,3-Diphenylisobenzofuran for Singlet Fission: Synthesis and Electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Akdag, Akin; Wahab, Abdul; Beran, Pavel; Rulíšek, Lubomír; Dron, P. I.; Ludvík, Jiří; Michl, Josef

    2015-01-01

    Roč. 80, č. 1 (2015), s. 80-89 ISSN 0022-3263 R&D Projects: GA ČR GA13-21704S; GA ČR(CZ) GA14-31419S Institutional support: RVO:61388963 ; RVO:61388955 Keywords : singlet fission * reduction potentials * electrochemistry * theoretical calculations Subject RIV: CC - Organic Chemistry; CG - Electrochemistry (UFCH-W) Impact factor: 4.785, year: 2015

  11. Electrochemistry of single molecules and biomolecules, molecular scale nanostructures, and low-dimensional systems

    DEFF Research Database (Denmark)

    Nazmutdinov, Renat R.; Zinkicheva, Tamara T.; Zinkicheva, Tamara T.

    2018-01-01

    Electrochemistry at ultra-small scales, where even the single molecule or biomolecule can be characterized and manipulated, is on the way to a consolidated status. At the same time molecular electrochemistry is expanding into other areas of sophisticated nano- and molecular scale systems includin...... molecular scale metal and semiconductor nanoparticles (NPs) and other nanostructures, e.g. nanotubes, “nanoflowers” etc.. The new structures offer both new electronic properties and highly confined novel charge transfer environments....

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  14. Direction des Etudes et Recherches Annual report 1980

    International Nuclear Information System (INIS)

    1981-01-01

    In this report the Study and Research Management of Electricite de France present the activities of 1980 as well as those to be developed in future. It describes the studies already carried out on the natural energies such as solar energy, the wind and geothermal energies and on the nuclear programme. They are continuing with, in addition, studies on the man-machine relationship, control robots, the safety and testing of materials. This diversification will co-exist with sustained action in the public service sector [fr

  15. DEVELOPMENT OF INTEGRATED ELECTROCHEMISTRY TEACHING MATERIAL BASED CONTEXTUAL FOR VOCATIONAL HIGH SCHOOL IN MACHINE ENGINEERING DEPARTEMENT

    Directory of Open Access Journals (Sweden)

    Wiwik Widodo

    2017-10-01

    Full Text Available The chemistry teaching at Vocational High School which tends to be theoretical and not directly connected to vocational lesson has caused students to have low interest, low motivation, and low achievement. The problem is becoming more complex due to limited time allotment and limited teaching materials. One of the efforts to solve the problem is by providing the relevant teaching material using contextual learning approach. The aims of this Research and Development (R&D research are: (1 to produce an appropriate chemistry teaching material on electrochemistry integrated with skill program subjects using Contextual approach for Vocational High School students of Machinery Engineering Department; (2 to know the feasibility of development result of teaching material. The development of the teaching material uses the 4D developmental model from Thiagarajan et al consisting of four phases namely Define, Design, Develop, and Desiminate. The dominate phase was not done. The scores of evaluation of the feasibility or the appropriateness of the product from the content expert are 88.75% (very feasible for the teachers’ book and 91.25% (very feasible for the students’ book. The expert on media gave 89.25% (very feasible for the teachers’ book and 89.9% (very feasible for the students’ book. The result of readability test shows that the teachers’ book is feasible (83.81% and the students’ book is very feasible (93.61%.

  16. Detailed H2 and CO Electrochemistry for a MEA Model Fueled by Syngas

    KAUST Repository

    Lee, W. Y.

    2015-07-17

    © The Electrochemical Society. SOFCs can directly oxidize CO in addition to H2, which allows them to be coupled to a gasifier. Many membrane-electrode-assembly (MEA) models neglect CO electrochemistry due to sluggish kinetics and the water-gas-shift reaction, but CO oxidation may be important for high CO-content syngas. The 1D-MEA model presented here incorporates detailed mechanisms for both H2 and CO oxidation, individually fitted to experimental data. These mechanisms are then combined into a single model, which provides a good fit to experimental data for H2/CO mixtures. Furthermore, the model fits H2/CO data best when a single chargetransfer step in the H2 mechanism is assumed to be rate-limiting for all current densities. This differs from the result for H2/H2O mixtures, where H2 adsorption becomes rate-limiting at high current densities. These results indicate that CO oxidation cannot be neglected in MEA models running on CO-rich syngas, and that CO oxidation can alter the H2 oxidation mechanism.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

  19. PENULISAN ETUDE-ETUDE MUSIK TALEMPONG UNGGAN (Sebuah Usaha Pembelajaran Musik Tradisi Berbasis Literatur

    Directory of Open Access Journals (Sweden)

    Asri MK

    2014-12-01

    Full Text Available “Talempong unggan”, a traditional music from Minangkabau community particularly in Unggan, Sumpur Kudus, Sijunjung Regency, West Sumatera Indonesia is classified into genre of “talempong duduak” (rea. Due to its special musical concept and the playing technics, this traditional music is selected as a practising course in the Karawitan Department of Indonesian Institute of Art (ISI Padang Panjang since 1993 till now. In a system of class learning with many students, Talempong Unggan definitely needs supporting methods and learning technics suitable for the course where the students can reach their maximum skills. All the melody of “talempong unggan” that has been made as a material of practice is transcribed to the system of numeric notation and rhythm motive of “gendang” and “aguang” which is written into signs and special notation. All of qualitative data is formulated into finding methods, technics and etude of learning ensamble of Talempong Unggan the traditional music that learned in Karawitan Department of ISI Padang Panjang. Key words: Talempong Unggan, Methods, Technics, Etude

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

    Science.gov (United States)

    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

  1. Electrochemistry of a ferrocene-grafted cell-penetrating peptide

    International Nuclear Information System (INIS)

    Messina, Pierluca; Hallais, Géraldine; Labbé, Eric; Béranger, Marie; Chassaing, Gérard; Lavielle, Solange; Mansuy, Christelle; Buriez, Olivier

    2012-01-01

    A cationic cell-penetrating peptide (CPP) labeled with both a ferrocenyl (Fc) moiety and a biotin (B) was successfully synthesized and investigated by electrochemistry. This original CPP derivative noted as Fc-CPP-B could be electrochemically detected, at a micromolar concentration, at a naked gold bead electrode. The presence of a biotin tag in the Fc-CPP-B complex allowed its complexation with avidin, which was itself tethered to a thiolated self-assembled monolayer. Such an avidin-modified gold surface, characterized by atomic force microscopy (AFM), allowed the immobilization of Fc-CPP-B onto the electrode surface, which greatly enhanced its electrochemical detection. Nevertheless, under these conditions the electrogenerated ferrocenium cation could not be reduced during the backward scan, indicating its unexpected reactivity when tethered within the avidin environment. In terms of detection and redox probe regeneration the best results were obtained at a glassy carbon electrode modified with a cation-exchange polymer. Ion-exchange voltammetry, performed under these conditions, allowed the pre-concentration of the peptide at the electrode surface thanks to the net positive charge of the CPP derivative. Interestingly, the anionic character of the polymer contributed to retain the electrogenerated cation Fc + in the film so that it could be reduced back to its original neutral form during the reverse voltammetric scans.

  2. 2006 Electrochemistry Gordon Research Conference - February 12-17-2006

    Energy Technology Data Exchange (ETDEWEB)

    Abruna, Hector D. [Cornell Univ., Ithaca, NY (United States)

    2007-04-03

    The Gordon Research Conference (GRC) on Electrochemistry was held at Santa Ynez Valley Marriott, Buellton California from February 12-17, 2006. The Conference was well-attended with 113 participants (attendees list attached). The attendees represented the spectrum of endeavor in this field coming from academia, industry, and government laboratories, both U.S. and foreign scientists, senior researchers, young investigators, and students. In designing the formal speakers program, emphasis was placed on current unpublished research and discussion of the future target areas in this field. There was a conscious effort to stimulate lively discussion about the key issues in the field today. Time for formal presentations was limited in the interest of group discussions. In order that more scientists could communicate their most recent results, poster presentation time was scheduled. Attached is a copy of the formal schedule and speaker program and the poster program. In addition to these formal interactions, "free time" was scheduled to allow informal discussions. Such discussions are fostering new collaborations and joint efforts in the field.

  3. Electrochemistry of Pt (100) in alkaline media: A voltammetric study

    Science.gov (United States)

    van der Vliet, Dennis F.; Koper, Marc T. M.

    2010-10-01

    Pt (100) is one of the fcc metal surface planes that reconstruct upon annealing at high temperatures. The state of the surface is important in electrochemistry, in order to correlate catalytic behavior with surface structure. Therefore, the behavior of single crystalline Pt (100) in alkaline media was investigated, with particular attention paid to surface long-range order. It was found that, in line with previous results, the manner of cooling the crystal after annealing influenced the state of surface significantly, with a profound effect on blank cyclic voltammetry as well as on carbon monoxide oxidation. Different ratios of inert and reductive gases were used to see if an optimal mixture could be obtained. Using air, argon, hydrogen, CO, and combinations of these gases gave rise to different states of the surface, with clear observable differences in blank voltammetric behavior and CO stripping. Also, the effect of alkali-metal cations and bromide on the blank and CO stripping voltammetry was investigated. Our main conclusion is that cooling in a carbon monoxide containing gas gives a clean, almost defect-free surface with long-range 1 × 1 symmetry. A similar surface can also be prepared with a hydrogen-containing cooling gas, but the content of hydrogen in that stream is critical.

  4. From supramolecular electrochemistry to molecular-level devices

    Energy Technology Data Exchange (ETDEWEB)

    Credi, Alberto; Ferrer Ribera, Belen; Venturi, Margherita

    2004-09-15

    Supramolecular (multi-component) systems can perform complex functions which result from the cooperation of actions performed by suitably selected molecular components. Looking at supramolecular systems, from the viewpoint of the functions, shows that the concept of macroscopic device can be extended to molecular level. Nature exploits very complex molecular-level devices to substain life, and, in the last twenty years, the development of supramolecular chemistry has allowed the construction of simple molecular-level devices, that are of interest not only for basic research, but also for the growth of nanoscience and nanotechnology. Molecular-level devices operate via electronic and/or nuclear rearrangements, and like macroscopic devices, they need energy to operate and signals to communicate with the operator. Electrochemistry can provide the answer to this dual requirement, since electrons/holes, besides supplying the energy needed to make a devices work, can also be useful to 'read' the state of the system and thus to control and monitor the operation of the device. In this article, some examples of molecular-level devices investigated in our laboratory will be reviewed.

  5. Electrochemistry of sulfur and polysulfides in ionic liquids.

    Science.gov (United States)

    Manan, Ninie S A; Aldous, Leigh; Alias, Yatimah; Murray, Paul; Yellowlees, Lesley J; Lagunas, M Cristina; Hardacre, Christopher

    2011-12-01

    The electrochemistry of elemental sulfur (S(8)) and the polysulfides Na(2)S(4) and Na(2)S(6) has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S(8) in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S(8) in [C(4)mim][DCA] ([C(4)mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as S(6)(2-) and S(4)(2-), and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S(6)(2-) and S(4)(2-) appears to be slow in the ionic liquid, with only small amounts of the blue radical species S(3)(•-) formed in the solutions at r.t., in contrast with that observed in most molecular solvents. © 2011 American Chemical Society

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

    Science.gov (United States)

    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%.

  7. A study of the aptitude of soils under natural conditions to retain radiostrontium; Etude de la vocation des sols en place a la retention du radiostrontium

    Energy Technology Data Exchange (ETDEWEB)

    Bovard, P; Grauby, A [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    Independently of the theoretical study of the propagation of radioactivity in the soil as a result of submersions or of radioactive rain, the authors have studied directly and practically how this radioactivity can vary in the actual soil. To this end a simple, rapid method has been perfected; it makes it possible to maintain for each soil sample the natural parameters (structure, humidity, etc.) without introducing boundary effects. In the laboratory, after charging the soil samples, part of the study of the propagation of radioactivity is done by autoradiography; finally, as a practical application, the study of an atomic site illustrates the methods described. (author) [French] Independamment de l'etude theorique de la propagation de la radioactivite dans le sol a la suite de submersions ou de pluies radioactives, les auteurs ont etudie directement et pratiquement comment pourrait evoluer cette radioactivite dans les sols en place. Pour cela, une methode simple et rapide a ete mise au point; elle permet de conserver pour chaque echantillon de sol, les parametres naturels (structure, humidite, etc...), sans introduire d'effets de paroi. En laboratoire, apres mise en charge des massifs preleves, une partie de l'etude de la propagation des radioelements est realisee par autoradiographie; enfin, une application pratique, l'etude d'un site atomique, illustre l'expose. (auteur)

  8. A study of the aptitude of soils under natural conditions to retain radiostrontium; Etude de la vocation des sols en place a la retention du radiostrontium

    Energy Technology Data Exchange (ETDEWEB)

    Bovard, P.; Grauby, A. [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    Independently of the theoretical study of the propagation of radioactivity in the soil as a result of submersions or of radioactive rain, the authors have studied directly and practically how this radioactivity can vary in the actual soil. To this end a simple, rapid method has been perfected; it makes it possible to maintain for each soil sample the natural parameters (structure, humidity, etc.) without introducing boundary effects. In the laboratory, after charging the soil samples, part of the study of the propagation of radioactivity is done by autoradiography; finally, as a practical application, the study of an atomic site illustrates the methods described. (author) [French] Independamment de l'etude theorique de la propagation de la radioactivite dans le sol a la suite de submersions ou de pluies radioactives, les auteurs ont etudie directement et pratiquement comment pourrait evoluer cette radioactivite dans les sols en place. Pour cela, une methode simple et rapide a ete mise au point; elle permet de conserver pour chaque echantillon de sol, les parametres naturels (structure, humidite, etc...), sans introduire d'effets de paroi. En laboratoire, apres mise en charge des massifs preleves, une partie de l'etude de la propagation des radioelements est realisee par autoradiographie; enfin, une application pratique, l'etude d'un site atomique, illustre l'expose. (auteur)

  9. go to top Electrochemistry and Spectroscopy of an Energetic Material FOX-7. A molecular Approach to Degradation Mechanism

    Czech Academy of Sciences Publication Activity Database

    Šimková, Ludmila; Urban, Jiří; Klíma, Jiří; Ludvík, Jiří

    2012-01-01

    Roč. 4, č. 6 (2012), s. 554-560 ISSN 2035-1755 R&D Projects: GA MŠk ME09002 Institutional support: RVO:61388955 Keywords : 2,2-Dinitroethene-1,1-Diamine * Degradation Mechanism * Electrochemistry Subject RIV: CG - Electrochemistry

  10. Dinuclear hexamethylbenzene ruthenium cations containing eta(1):eta(2)-2-(ferrocenyl)ethen-1-yl ligands: Synthesis, structure, electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Tschan, M. J.-L.; Therrien, B.; Ludvík, Jiří; Štěpnička, P.; Süss-Fink, G.

    2006-01-01

    Roč. 691, č. 20 (2006), s. 4304-4311 ISSN 0022-328X Institutional research plan: CEZ:AV0Z40400503 Keywords : arene ligands * electrochemistry * ferrocene derivatives Subject RIV: CG - Electrochemistry Impact factor: 2.332, year: 2006

  11. Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Govindaswamy, P.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

    2007-01-01

    Roč. 692, č. 8 (2007), s. 1661-1671 ISSN 0022-328X R&D Projects: GA MŠk LC510; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : dinuclear complexes * iridium * rhodium * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

  12. Board and card games for studying electrochemistry: Preliminary research and early design

    Science.gov (United States)

    Kurniawan, Rizmahardian Ashari; Kurniasih, Dedeh; Jukardi

    2017-12-01

    Games in the chemistry classroom can offer engaging and fun alternative method of learning. However, only a few games in chemistry, especially in electrochemistry subject are available commercially. In this research, we developed board and card games for studying electrochemistry. We surveyed chemistry teacher and students from 10 different senior high schools in Pontianak to decide content and characteristic of the game. We have designed the game that can be played by four students or four group of students, either as a specific instruction in the classroom or as a supplementary learning material. The game was designed to help students understanding the voltaic cell configuration and its voltaic potential.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  14. Application on electrochemistry measurement of high temperature high pressure condition in PWR nuclear power plants

    International Nuclear Information System (INIS)

    Li Yuchun; Xiao Zhongliang; Jiang Ya; Yu Xiaowei; Pang Feifei; Deng Fenfang; Gao Fan; Zhou Nianguang

    2011-01-01

    High temperature high pressure electrochemistry testing system was comprehensively analyzed in this paper, according to actual status for supervision in primary and secondary circuits of PWR nuclear power plants. Three research methods were reviewed and discussed for in-situ monitor system. By combination with ECP realtime measurement it was executed for evaluation and water chemistry optimization in nuclear power plants. It is pointed out that in-situ electrochemistry measurement has great potential application for water chemistry evaluation in PWR nuclear power plants. (authors)

  15. STM, SECPM, AFM and Electrochemistry on Single Crystalline Surfaces

    Directory of Open Access Journals (Sweden)

    Ulrich Stimming

    2010-08-01

    Full Text Available Scanning probe microscopy (SPM techniques have had a great impact on research fields of surface science and nanotechnology during the last decades. They are used to investigate surfaces with scanning ranges between several 100 mm down to atomic resolution. Depending on experimental conditions, and the interaction forces between probe and sample, different SPM techniques allow mapping of different surface properties. In this work, scanning tunneling microscopy (STM in air and under electrochemical conditions (EC-STM, atomic force microscopy (AFM in air and scanning electrochemical potential microscopy (SECPM under electrochemical conditions, were used to study different single crystalline surfaces in electrochemistry. Especially SECPM offers potentially new insights into the solid-liquid interface by providing the possibility to image the potential distribution of the surface, with a resolution that is comparable to STM. In electrocatalysis, nanostructured catalysts supported on different electrode materials often show behavior different from their bulk electrodes. This was experimentally and theoretically shown for several combinations and recently on Pt on Au(111 towards fuel cell relevant reactions. For these investigations single crystals often provide accurate and well defined reference and support systems. We will show heteroepitaxially grown Ru, Ir and Rh single crystalline surface films and bulk Au single crystals with different orientations under electrochemical conditions. Image studies from all three different SPM methods will be presented and compared to electrochemical data obtained by cyclic voltammetry in acidic media. The quality of the single crystalline supports will be verified by the SPM images and the cyclic voltammograms. Furthermore, an outlook will be presented on how such supports can be used in electrocatalytic studies.

  16. Martian Dust Devil Electron Avalanche Process and Associated Electrochemistry

    Science.gov (United States)

    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.

  17. Implementing Formative Assessment in Engineering Education: The Use of the Online Assessment System Etude

    Science.gov (United States)

    Dopper, Sofia M.; Sjoer, Ellen

    2004-01-01

    This article describes the possibilities offered by the online assessment system Etude to achieve the benefits of formative assessment. In order to find out the way this works in practice, we carried out an experiment with the use of Etude for formative assessment in the course on collaborative report writing. Results show that online formative…

  18. Electrochemistry of Single Metalloprotein and DNA‐Based Molecules at Au(111) Electrode Surfaces

    DEFF Research Database (Denmark)

    Salvatore, Princia; Zeng, Dongdong; Karlsen, Kasper Kannegård

    2013-01-01

    We have briefly overviewed recent efforts in the electrochemistry of single transition metal complex, redox metalloprotein, and redox‐marked oligonucleotide (ON) molecules. We have particularly studied self‐assembled molecular monolayers (SAMs) of several 5′‐C6‐SH single‐ (ss) and double‐strand (...

  19. Hydroxylamine electrochemistry at low-index single-crystal platinum electrodes in acidic media

    NARCIS (Netherlands)

    Rosca, V.; Beltramo, G.L.; Koper, M.T.M.

    2004-01-01

    The electrochemistry of hydroxylamine at low-index single-crystal platinum electrodes in acidic media has been studied by voltammetry and in-situ FTIRRAS. Hydroxylamine (HAM) reactivity at platinum is largely controlled by interaction of the other components of the solution or products of the HAM

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

    NARCIS (Netherlands)

    van den Beld, Wesley T. E.; Odijk, Mathieu; Vervuurt, Rene 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

  1. Synthesis, Molecular Structure, and Electrochemistry of 1-Ferrocenyl-1,2-dicarba-closo-dodecaboranes

    Czech Academy of Sciences Publication Activity Database

    Korotvička, A.; Šnajdr, I.; Štěpnička, P.; Císařová, I.; Janoušek, Zbyněk; Kotora, M.

    -, č. 15 (2013), s. 2789-2798 ISSN 1434-1948 Grant - others:GA ČR(CZ) GAP207/11/0338; GAČR(CZ) GAP207/11/0705 Program:GA Institutional support: RVO:61388963 Keywords : carboranes * metallocenes * structure elucidation * electrochemistry * addition Subject RIV: CA - Inorganic Chemistry Impact factor: 2.965, year: 2013

  2. Isoflurane as a solvent for electrochemistry. Electrooxidation study of icosahedral carborane anions in four different solvents

    Czech Academy of Sciences Publication Activity Database

    Wahab, Abdul; Kvapilová, Hana; Klíma, Jiří; Michl, Josef; Ludvík, Jiří

    2013-01-01

    Roč. 689, JAN 2013 (2013), s. 257-261 ISSN 1572-6657 R&D Projects: GA MŠk ME09002; GA ČR GC203/09/J058 Institutional support: RVO:61388955 ; RVO:61388963 Keywords : isoflurane * relative permitivity * icosahedral carborane anions Subject RIV: CG - Electrochemistry Impact factor: 2.871, year: 2013

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

  5. Implementation of Case-Based Instruction on Electrochemistry at the 11th Grade Level

    Science.gov (United States)

    Tarkin, Aysegul; Uzuntiryaki-Kondakci, Esen

    2017-01-01

    This study aims to compare the effectiveness of case-based instruction over traditional instruction in improving 11th grade students' understanding of electrochemistry concepts, attitudes toward chemistry, chemistry self-efficacy beliefs, and motivation to learn chemistry. In total, 113 students (47 males and 66 females) from three high schools…

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

    Science.gov (United States)

    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…

  7. Application of ultrasound in electrochemistry. An overview of mechanisms and design of experimental arrangement

    Czech Academy of Sciences Publication Activity Database

    Klíma, Jiří

    2011-01-01

    Roč. 51, č. 2 (2011), s. 202-209 ISSN 0041-624X R&D Projects: GA MŠk LC510; GA MŠk 1P05OC074 Institutional research plan: CEZ:AV0Z40400503 Keywords : sonoelectrochemistry * mechanism of sonochemical effect * microjets Subject RIV: CG - Electrochemistry Impact factor: 1.838, year: 2011

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

    Science.gov (United States)

    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. Electrochemistry of Hemin on Single-Crystal Au(111)-electrode Surfaces

    DEFF Research Database (Denmark)

    Zhang, Ling; Ulstrup, Jens; Zhang, Jingdong

    adsorption on well-defined single-crystal Au(111)-electrode surfaces using electrochemistry combined with scanning tunnelling microscopy under electrochemical control. Hemin gives two voltammetric peaks assigned to adsorbed monomers and dimmers (Fig. 1B). In situ STM shows that hemin self...

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

    Science.gov (United States)

    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…

  11. Abrasive stripping voltammetry - a new method for the study of the electrochemistry of solid materials

    International Nuclear Information System (INIS)

    Scholz, F.

    1992-01-01

    The method is applicable to electronic conductors and non-conductors. The following applications are described: Qualitative and quantitative analysis of alloys, identification of minerals, quantitative analysis of powder mixtures, identification and study of the electrochemistry of different phases in high-T c superconductor systems, determination of stability constants of metal dithiocarbamates, study of the corrosion behaviour of dental alloys. (orig.)

  12. Electrochemistry at the edge of a single graphene layer in a nanopore

    DEFF Research Database (Denmark)

    Banerjee, Sutanuka; Shim, Jeong; Rivera, J.

    2013-01-01

    We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and AlO 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 a unique...

  13. In-situ Liquid Electron Microscopy Setups for Investigation of Nanoscale Electrochemistry

    DEFF Research Database (Denmark)

    Jensen, Eric; Møller-Nilsen, Rolf Erling Robberstad; Canepa, Silvia

    2014-01-01

    -situ electrochemistry and has achieved ~10 nm resolution. Such systems are important tools for developing sustainable technology and for understanding nanoscale phenomena. However, both systems suffer from interacting with theelectron beam, which is a high-voltage radiation source, and therefore initial experiments...

  14. 98 Etude Comparative du Systeme Phonematique et Tonal des ...

    African Journals Online (AJOL)

    98. Etude Comparative du Systeme Phonematique et Tonal des. Deux Parlers: Le Yoruba du Nigeria et L'itsa Parle en. Republique du Benin. Ajani Akinwumi Lateef et Ayuba G. Ajibabi http://dx.doi./org/10.4314/ujah.v18i3.5. Résume. En ce début de l'époque ou la mondialisation et la coexistence des peuples dans le ...

  15. Nuclear study of Melusine; Etude nucleaire de Melusine

    Energy Technology Data Exchange (ETDEWEB)

    Cherot, J [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1959-07-01

    In this report are reviewed - with respect to starting of experiments - the main nuclear characteristics of a 20 per cent enriched uranium lattice, with light water as moderator and reflector. The reactor is to operate at 1 MW. 1) Study of various critical masses. 2) Control. Effectiveness of cadmium. Control rods and of a stainless steel regulating rod. 3) Study of the effect on reactivity of disturbances in the core center. 4) Study of xenon and samarium poisoning. 5) Temperature factor. 6) Heat exchanges in a fuel element. (author) [French] On etudie, dans ce rapport, les principales proprietes nucleaires d'un reseau a uranium enrichi (20 pour cent), dont le moderateur et le reflecteur sont l'eau legere en vue des experiences de demarrage. Ce reacteur devra fonctionner a 1 MW. 1) Etude de diverses masses critiques. 2) Controle. Efficacite des barres de controle en cadmium et d'une barre de reglage en acier inoxydable. 3) Etude de l'effet sur la reactivite de perturbation au centre du coeur. 4) Etude de l'empoisonnement xenon et samarium. 5) Coefficient de temperature. 6) Echanges thermiques dans un element. (auteur)

  16. Study of a device for the direct measurement of the fission gas pressure inside an in-pile fuel element; Etude d'un dispositif pour la mesure directe de la pression des gaz de fission a l'interieur d'un element combustible en pile

    Energy Technology Data Exchange (ETDEWEB)

    Lavaud, B; Uschanoff, S [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-07-01

    The fission gas pressure inside a fuel element made of a refractory fuel constitutes an important limiting factor for the burn-up. Although it is possible to calculate approximately the volume of gas produced outside the fuel during its life-time; it is nevertheless very difficult to evaluate the pressure since the volume allowed to the fission gases, as well as their temperature are known only very approximately. This physical value, which is essential for the technologist, can only be known by direct in-pile measurement of the pressure. The report describes the equipment which has been developed for this test. (authors) [French] La pression des gaz de fission a l'interieur d'un element combustible a combustible refractaire constitue une des limitations importantes du taux de combustion. Si on peut approcher par calcul la determination du volume, des gaz degages hors du combustible au cours de sa vie, il est par contre tres difficile d'evaluer la pression car le volume alloue aux gaz de fission et leur temperature sont tres mal connus. Cette donnee essentielle pour le technologue ne peut etre atteinte que par une mesure directe en pile de la pression. Le rapport decrit l'appareillage qui a ete mis au point pour cet essai. (auteurs)

  17. Study of direct Cp violation in B decay into vector mesons including rho zero-omega mixing in the framework of the LHCb experiment; Etude de la violation directe de CP dans la desintegration du meson B en mesons vecteurs incluant le melange {rho}{sup 0} - {omega} dans le cadre de l'experience LHCb

    Energy Technology Data Exchange (ETDEWEB)

    Rimbault, C

    2004-02-01

    {rho}{sub 0} - {omega} mixing effect on direct CP violation in B decay into vector mesons is one of the main studies of this work. The first part is dedicated to the calculation of the decay amplitudes of the channels B {yields} V{rho}{sup 0}({omega}) which have been represented by a model. We have used the helicity formalism. In such a way branching ratios and asymmetries depending on form factor models and other parameters are predicted. Direct CP violation appears at several levels: in branching ratios, in angular distributions and in differential asymmetry as a function of {rho}{sup 0} - {omega} mass. The dominance of the longitudinal polarization in the studied channels is confirmed by Babar and Belle experimental results. We calculated too the strong phase and the ratio of Penguin to Tree amplitudes for each channel. In a second part, was developed an analysis of the channel B{sup 0} {yields} K{sup *0}{rho}{sup 0}({omega}) in the framework of LHCb experiment. It will start in 2007 and is dedicated to b flavor study and CP violation. The realistic analysis which has been performed shows that this channel is not appropriate to observe {rho}{sup 0} - {omega} mixing effect on asymmetry in LHCb, while the {rho}{sup +}{rho}{sup 0}({omega}) channel, for which we have predicted a branching ratio value confirmed by Babar and Belle, is much more promising. (author)

  18. 'DIRECT DISPOSAL'. Comparative study of the radiological risk of the spent fuel and vitrified waste disposals in granite deep geological formation; 'STOCKAGE DIRECT'. Etude comparative du risque radiologique des stockages de combustibles uses et de dechets vitrifies en formation geologique profonde de type granitique

    Energy Technology Data Exchange (ETDEWEB)

    Baudoin, Patrick; Gay, Didier [Departement d' evaluation de surete, Inst. de Protection et de Surete Nucleaire, CEA Centre d' Etudes de Fontenay-aux-Roses, 92 (France)

    1996-09-01

    In order to study the implications of a possibly 'direct disposal' of the spent fuel a working group has been created in 1991. This report gives an evaluation of the radiological impact as well as of the technical and economical characteristics of a generic disposal scenario for untreated spent fuel. The basic scheme implies a temporary storage and, then after an adequate preparation, the disposal in a deep geological formation. This document concerning the evaluation of the radiological impact associated to the geological disposal of the spent fuel constitutes the IPSN's contribution to the report of working group. The solution, as defined by the group, specifies the disposal of multifunctional TSD containers ensuring the Transport, Storage and final Disposal in mine drifts of granite formation. Two values for amounts to be stored were taken into account: one corresponds to 43,500 fuel assemblies of PWR UOX type irradiated at 33,000 MWd.t{sup -1}, while the other, corresponds to 20,400 assemblies of the same type. The radiological risk was evaluated for two distinct evolution scenarios, one supposing the preservation of initial characteristics of the disposal site, the other supposing alterations like those induced by drilling deep water wells in the disposal's vicinity. The individual effective dose were computed for each of these scenarios. Also, a comparison is made between the case of direct disposal of spent fuels and the case of disposal of reprocessed fuels of the same type.

  19. Etudes théoriques et expérimentales de la combustion dans les moteurs Diesel d'automobiles à injection directe et à préchambre Theoretical and Experimental Research on Combustion in Diesel Automotive Engines with Direct Injection and a Prechamber

    Directory of Open Access Journals (Sweden)

    Douaud A.

    2006-11-01

    Full Text Available Certaines techniques récemment développées pour la modélisation mathématique et les investigations expérimentales sur moteur Diesel sont présentées. On insiste sur l'importance de la validation croisée entre calcul et mesure. Taux d'injection, aérodynamique interne, développement du spray sont analysés en relation avec la géométrie des chambres de combustion. Des exemples, portant principalement sur des considérations de rendement énergétiques et d'émissions polluantes sont présentés à la fois sur le moteur Diesel à préchambre et le moteur Diesel à injection directe. Various techniques developed recently for the mathematical modeling and experimental investigating of diesel engines are described. Emphasis is placed on the importance of crosschecking between computing and measuring. The injection rate, internal aerodynamics and spray development are analyzed in relation to the geometry of combustion chambers. Examples mainly concerning matters of energy efficiency and pollutant emissions are given for diesel engines both with a prechamber and with direct injection.

  20. Direct numerical simulation of two-phases turbulent combustion: application to study of propagation and structure of flames; Simulation numerique directe de la combustion turbulente diphasique: application a l'etude de la propagation et de la structure des flammes

    Energy Technology Data Exchange (ETDEWEB)

    Canneviere, K.

    2003-12-15

    This work is devoted to the study of the propagation and the structure of two-phases turbulent flames. To this end, Direct Numerical Simulations (DNS) are used. First, numerical systems for two-phases flow simulations is presented along with a specific chemical model. Then, a study of laminar spray flames is carried out. An analytical study related to the dynamics of evaporation of droplets is first proposed where the influence on the equivalence ratio of the ratio between the heating delay of the droplet and the evaporation delay is detailed. The simulation of a propagating flame through a cloud of droplets is carried out and a pulsating behavior is highlighted. A study of these flames according to the topology of liquid fuel enabled us to characterize a double flame structure composed of a premixed flame and a diffusion flame. Our last study is devoted to spray turbulent flames. Two-phase combustion of turbulent jets has been simulated. By varying the spray injection parameters (density, equivalence ratio), a database has been generated. This database allowed us to describe local and global flame regimes appearing in the combustion of sprays. They have been categorized in four main structures: open and closed external regime, group combustion and mixed combustion. Eventually, a combustion diagram has been developed. It involves the spray vaporization time, the mean inter-space between droplets or group of droplets and eventually the injected equivalence ratio. (author)

  1. Hydrogenated graphenes by birch reduction: influence of electron and proton sources on hydrogenation efficiency, magnetism, and electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Eng, A.Y.S.; Sofer, Z.; Huber, Š.; Bouša, D.; Maryško, Miroslav; Pumera, M.

    2015-01-01

    Roč. 21, č. 7 (2015), 16828-16838 ISSN 0947-6539 Institutional support: RVO:68378271 Keywords : hydrogenated graphenes * birch reduction * magnetism * electrochemistry * hydrogenation efficiency Subject RIV: CA - Inorganic Chemistry Impact factor: 5.771, year: 2015

  2. Feasibility of using of the second gradient theory for the direct numerical simulation of liquid-vapor flows with phase-change; Etude des potentialites de la theorie du second gradient pour la simulation numerique directe des ecoulements liquide-vapeur avec changement de phase

    Energy Technology Data Exchange (ETDEWEB)

    Jamet, D. [CEA Grenoble, 38 (France). Dept. de Thermohydraulique et de Physique]|[Ecole Centrale de Paris, 75 (France)

    1998-12-31

    One on the main difficulties encountered in the direct numerical simulation of two-phase flows in general and of liquid-vapor flows with phase-change in particular, is the interface tracking. The idea developed in this work consists in modeling a liquid-vapor interface as a volumetric zone across which physical properties vary continuously instead of a discontinuous surface. The second gradient theory allows to establish the evolution equations of the fluid in the whole system: bulk phases and interfaces. That means that the resolution of a unique system of partial differential equations is necessary to determine the whole two-phase flow, the interfaces and their evolution in time being a part of the solution of this unique system. We show in this work that it is possible to artificially enlarge an interface without changing its surface tension and the latent heat of vaporization. That means than it is possible to track all the interfaces of a liquid-vapor two-phase flow with phase-change on a mesh the size of which is imposed by the smallest Kolmogorov scale of the bulk phases for example. The artificial enlargement of an interfacial zone is obtained by modifying the thermodynamic behavior of the fluid within the binodal. We show that this modification does not change the dynamics of an interface. However, although the thickness of an interface and its surface tension vary with the mass and heat fluxes that go though it, the thermodynamic modification necessary to the artificial enlargement of an interface drastically increases these variations. Consequently, the artificial enlargement of an interface must be made carefully to avoid a too much important variation of its surface tension during dynamic situations. (author) 60 refs.

  3. Study of the droplet size of sprays generated by swirl nozzles dedicated to gasoline direct injection: measurement and application of the maximum entropy formalism; Etude de la granulometrie des sprays produits par des injecteurs a swirl destines a l'injection directe essence: mesures et application du formalisme d'entropie maximum

    Energy Technology Data Exchange (ETDEWEB)

    Boyaval, S.

    2000-06-15

    This PhD presents a study on a series of high pressure swirl atomizers dedicated to Gasoline Direct Injection (GDI). Measurements are performed in stationary and pulsed working conditions. A great aspect of this thesis is the development of an original experimental set-up to correct multiple light scattering that biases the drop size distributions measurements obtained with a laser diffraction technique (Malvern 2600D). This technique allows to perform a study of drop size characteristics near the injector tip. Correction factors on drop size characteristics and on the diffracted intensities are defined from the developed procedure. Another point consists in applying the Maximum Entropy Formalism (MEF) to calculate drop size distributions. Comparisons between experimental distributions corrected with the correction factors and the calculated distributions show good agreement. This work points out that the mean diameter D{sub 43}, which is also the mean of the volume drop size distribution, and the relative volume span factor {delta}{sub v} are important characteristics of volume drop size distributions. The end of the thesis proposes to determine local drop size characteristics from a new development of deconvolution technique for line-of-sight scattering measurements. The first results show reliable behaviours of radial evolution of local characteristics. In GDI application, we notice that the critical point is the opening stage of the injection. This study shows clearly the effects of injection pressure and nozzle internal geometry on the working characteristics of these injectors, in particular, the influence of the pre-spray. This work points out important behaviours that the improvement of GDI principle ought to consider. (author)

  4. Electrochemistry and in situ Raman spectroelectrochemistry of low and high quality boron doped diamond layers in aqueous electrolyte solution

    Czech Academy of Sciences Publication Activity Database

    Vlčková Živcová, Zuzana; Frank, Otakar; Petrák, Václav; Tarábková, Hana; Vacík, Jiří; Nesládek, M.; Kavan, Ladislav

    2013-01-01

    Roč. 87, JAN 2013 (2013), s. 518-525 ISSN 0013-4686 R&D Projects: GA AV ČR IAA400400804; GA AV ČR KAN200100801 Grant - others:European Commission CORDIS(XE) FP7-ENERGY-2010-FET, projekt 256617 Institutional support: RVO:61389005 ; RVO:61388955 ; RVO:68378271 Keywords : boron doped diamond * electrochemistry * aqueous electrolyte solution Subject RIV: CG - Electrochemistry Impact factor: 4.086, year: 2013

  5. Polycrystalline TiO2 Anatase with a Large Proportion of Crystal Facets (001): Lithium Insertion Electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Bouša, Milan; Lásková, Barbora; Zukalová, Markéta; Procházka, Jan; Chou, A.; Kavan, Ladislav

    2010-01-01

    Roč. 157, č. 10 (2010), A1108-A1112 ISSN 0013-4651 R&D Projects: GA MŠk LC510; GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : polycrystalline * TiO2 * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 2.420, year: 2010

  6. Composite system based on biomolecules-functionalized multiwalled carbon nanotube and ionic liquid: Electrochemistry and electrocatalysis of tryptophane

    International Nuclear Information System (INIS)

    Li Li; Bu Caihong; Zhang Yijun; Du Jie; Lu Xiaoquan; Liu Xiuhui

    2011-01-01

    The combination of biomolecules-functionalized multiwalled carbon nanotube (MWNTs) and ionic liquid (IL) yields nanostructured biointerfaces, formed a novel kind of structurally uniform and bioelectrocatalytic activity material. Rutin was chosen as a model biomolecules to investigate the composite system. The MWNTs–Rutin–IL composite film was characterized by different methods including thermogravimetric analysis (TGA), UV–vis spectra, electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscope (SECM). A pair of well-defined quasi reversible redox peaks of rutin was obtained at the MWNTs–Rutin–IL composite film modified glassy carbon electrode (GCE) by direct electron transfer between the rutin and the GCE electrode. Dramatically enhanced biocatalytic and electrocatalytic activity was exemplified at the MWNTs–Rutin–IL/GCE electrode by the oxidized of tryptophane. The oxidation peak currents of tryptophane in such modified electrode increased linearly with the concentrations of tryptophane in the range from 8 × 10 −8 to 2 × 10 −5 mol L −1 with a detection limit of 3.0 × 10 −8 mol L −1 . The unique composite material based on biomolecules-functionalized carbon nanotube and ionic liquid have wide potential applications in direct electrochemistry, biosensors, and biocatalysis.

  7. II Colombian Congress of Electrochemistry (CCEQ) and 2nd Symposium on Nanoscience and Nanotechnology (SNN)

    International Nuclear Information System (INIS)

    2017-01-01

    In the present volume of Journal of Physics: Conference Series we publish the proceedings of the “II Colombian Congress of Electrochemistry (CCEQ) and 2nd Symposium on Nanoscience and Nanotechnology (SNN)”, that was held from, October 4-7, 2016, at the Bucarica headquarters of the Universidad Industrial de Santander (UIS), Bucaramanga, Colombia. The proceedings consist of 45 contributions that were presented as plenary talks at the event. The abstracts of all participants’ contributions were published in the Abstract Book with ISBN 978-958-8819-39-6. The website of the symposium is available at http://cceq.uis.edu.co/. The scientific program of the II CCEQ and 2nd SNN consisted of 5 Plenary Lecture, 3 Magisterial Conferences, 2 Keynote, 54 Oral and 78 Poster Presentations and 3 Courses with the participation of undergraduate and graduate students, professors, researchers and entrepreneurs from Colombia, Spain, Mexico, Brazil and Venezuela. Moreover, the II CCEQ and 2nd SNN provided a forum of exchange in the research and innovation that enrich the area of electrochemistry, Nanoscience and Nanotechnology of the materials and the industrial applications. All papers in these Proceedings refer to one from the following topics: New Materials, Thin Film, Surface Physics, Simulation and Diagnosis, Laser and Hybrid Processes, Biomedical Coatings, Preparation/Characterization/Application Nanomaterials, Surface Modification (Ionic Implantation, Ion Nitriding, PVD, CVD), Electrochemistry of Materials (Electrodeposits, Electropolymerization, Nanoelectrochemistry, Semiconductors), Corrosion, Analytical Electrochemistry, Electrochemistry in Mineral Processing and Metals (Extractive Metallurgy), Storage and Conversion Electrochemical Energy and Environmental Electrochemistry and Water Treatment involving Electrochemical Nature Phenomena. The editor hopes that those interested in the area of the science of materials can to enjoy this reading that reflects a wide variety of

  8. Magnetite-graphene for the direct electrochemistry of hemoglobin and its biosensing application

    Energy Technology Data Exchange (ETDEWEB)

    He Yaping; Sheng Qinglin [Institute of Analytical Science/Shaanxi Provincial Key Laboratory of Electroanalytical Chemistry, Northwest University, Xi' an, Shaanxi 710069 (China); Zheng Jianbin, E-mail: zhengjb@nwu.edu.c [Institute of Analytical Science/Shaanxi Provincial Key Laboratory of Electroanalytical Chemistry, Northwest University, Xi' an, Shaanxi 710069 (China); Wang Minzhi [Institute of Analytical Science/Shaanxi Provincial Key Laboratory of Electroanalytical Chemistry, Northwest University, Xi' an, Shaanxi 710069 (China); Liu Bin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), Northwest University, Xi' an, Shaanxi 710069 (China); Department of Chemistry, Xianyang Normal University, Xianyang, Shaanxi 712000 (China)

    2011-02-01

    Magnetite-graphene (Fe{sub 3}O{sub 4}-GE) was prepared via a simple effective chemical precipitation method, followed by the chemical reduction with hydrazine. Fe{sub 3}O{sub 4}-GE was characterized by Raman spectroscopy, transmission electron microscope, X-ray powder diffraction and electrochemical methods. A hydrogen peroxide (H{sub 2}O{sub 2}) biosensor was structured by immobilizing hemoglobin (Hb) into Fe{sub 3}O{sub 4}-GE for the first time. UV-vis and Fourier transform infrared spectra were employed to characterize Hb retained original structure in the resulting Hb-Fe{sub 3}O{sub 4}-GE membrane. Electrochemical investigation of the biosensor showed a pair of well-defined, quasi-reversible redox peaks with E{sub pa} = -0.285 V and E{sub pc} = -0.363 V (vs. SCE) in phosphate buffer solution (0.1 mol/L, pH 7.0) at the scan rate of 100 mV/s. The Hb-Fe{sub 3}O{sub 4}-GE showed a better synergistic electrochemical effect for the reduced process of H{sub 2}O{sub 2}. The biosensor displayed a fast response time (<3 s) and broad linear response to H{sub 2}O{sub 2} in the range from 1.50 to 585 {mu}mol/L with a relatively low detection limit of 0.5 {mu}mol/L (S/N = 3). Moreover, the biosensor could be applied in practical analysis and exhibit good reproducibility and long-term stability.

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    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 pH 6.0. The electron-transfer coefficient (α), electron transfer number (n), and electrode reaction rate constant (Κs) were calculated as 0.78, 0.73, and 4.63 s −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%. - Graphical abstract: Schematic diagram of the synthesis of MrGO hybrid and the fabrication process of the MrGO/Nafion/GCE for determination of lobetyolin. Display Omitted - Highlights: • The MrGO/Nafion@GCE electrochemical sensor was successfully fabricated. • The prepared MrGO was characterized by AFM, XRD, FTIR, VSM, TEM and SEM. • The proposed electrochemical sensor exhibited a broad detection range and low detection limit for lobetyolin. • The electrochemical sensor can be used for the sensitive and efficient analysis of lobetyolin in real samples.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Bolu [School of Pharmacy, Lanzhou University, Lanzhou 730000 (China); Gou, Xiaodan [School of Chemistry and Chemical Engineering, Nanjing University, 210046 (China); Bai, Ruibin; Abdelmoaty, Ahmed Attia Ahmed; Ma, Yuling; Zheng, Xiaoping [School of Pharmacy, Lanzhou University, Lanzhou 730000 (China); Hu, Fangdi, E-mail: hufd@lzu.edu.cn [School of Pharmacy, Lanzhou University, Lanzhou 730000 (China)

    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 pH 6.0. The electron-transfer coefficient (α), electron transfer number (n), and electrode reaction rate constant (Κs) were calculated as 0.78, 0.73, and 4.63 s{sup −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{sup −7} to 1.0 × 10{sup −4} mol/L with detection limit (S/N = 3)of 4.3 × 10{sup −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%. - Graphical abstract: Schematic diagram of the synthesis of MrGO hybrid and the fabrication process of the MrGO/Nafion/GCE for determination of lobetyolin. Display Omitted - Highlights: • The MrGO/Nafion@GCE electrochemical sensor was successfully fabricated. • The prepared MrGO was characterized by AFM, XRD, FTIR, VSM, TEM and SEM. • The proposed electrochemical sensor exhibited a broad detection range and low detection limit for lobetyolin. • The electrochemical sensor can be used for the sensitive and efficient analysis of lobetyolin in real samples.

  11. The use radioactive tracers in the study of solid transport in water streams; Emploi de traceurs radioactifs pour l'etude du transport solide dans les cours d'eau

    Energy Technology Data Exchange (ETDEWEB)

    Courtois, G [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires; Jaffry, P; Heuzel, M [Laboratoire National d' Hydraulique de Chatou, 78 (France)

    1960-07-01

    The Laboratoire National d'Hydraulique which has been studying, during the last few years in conjunction with the Centre d'Etudes Nucleaires at Saclay, the development of apparatus and of methods of investigation of sediment transport by radioactive tracer techniques, is at the moment trying to perfect a genuinely quantitative method of investigation. Two experiments have recently been carried out in rivers, the first designed to investigate the transport of pebbles in the river Rhone, the other to investigate the movement of sands in the Niger. This second experiment has been supported by parallel experiments carried out on a reduced scale model of the Niger built at the laboratories of Chatou: in this experiment are used the radiation from {sup 56}Mn and {sup 24}Na obtained by direct activation of the crushed apricot store which represents, in the scale model, the natural sediment on the bed of the Niger. The combined efforts of the laboratories of Chatou and of the Centre d'Etudes Nucleaires at Saclay are at the moment directed to the application of radioactive tracers to studies on the scale models with the double aim: a) of having a single investigational method for the actual experiment and for the model making it possible to control the accuracy of the model in the preliminary stage of calibrating this model; b) of making the most of the possibilities of observation and of direct measurement offered by the scale models for studying the possibility of improving the tracer method, in particular with respect to the collecting of quantitative data. (author) [French] La Laboratoire National d'Hydraulique qui, depuis quelques annees a developpe, en collaboration avec le Centre d'Etudes Nucleaires de Saclay, les appareillages et les techniques d'etudes des mouvements de sediments par la methode des traceurs radioactifs, s'efforce actuellement de mettre au point un moyen d'investigation veritablement quantitatif. Deux experiences ont ete effectuees recemment en

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

    Energy Technology Data Exchange (ETDEWEB)

    Kinoshita, K. [ed.] [Lawrence Berkeley National Lab., CA (United States); Scherson, D. [ed.] [Case Western Reserve Univ., Cleveland, OH (United States)

    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.

  13. Development of a controlled-distance electrochemistry arrangement to be used in power plant environments

    International Nuclear Information System (INIS)

    Bojinov, M.; Laitinen, T.; Moilanen, P.; Maekelae, K.; Maekelae, M.; Saario, T.; Sirkiae, P.

    2000-07-01

    This publication presents the state-of-the-art of the controlled-distance electrochemistry (CDE) arrangement developed at VTT. Due to the possibility to control accurately the distance between two electrodes, the CDE arrangement makes possible electrochemical measurements in poorly-conductive media such as simulated coolants of light water reactor systems. This experimental arrangement has now been developed into a versatile electrochemical tool, which can be used for thin-layer electrochemistry (TLEC), wall-jet ring-disc and contact electric impedance (CEI) as well as contact electric resistance (CER) measurements. This report comprises results from the years 1997-1999 and summarises the different possible TLEC configurations and electrode locations as well as the development of a bellows-driven CDE system. (orig.)

  14. Proceedings of the eleventh ISEAC international discussion meet on electrochemistry and its applications

    International Nuclear Information System (INIS)

    Aggarwal, Suresh K.; Guin, Saurav K.; Gupta, Ruma S.; Ambolikar, Arvind S.

    2014-01-01

    Electrochemistry has truly emerged as a multidisciplinary science and is being used in different fields for variety of applications. Several electrochemically synthesized nano composites of conducting polymers and nanoparticles of noble metals are promising electrode materials in fuel cells because of their electrocatalytic behavior. Room Temperature Ionic Liquids (RTILs) are the green solvents which have generated a lot of interest because of their broad electrochemical window which allows the reduction of ions with very high negative redox potentials on Pt, Au, glassy carbon electrodes etc., without significant hydrogen evolution. Therefore, RTILs are promising electrolytes for electrochemical studies on actinides and lanthanides. This issue includes two tutorial articles viz. Carbon nanotubes and its significance in electrochemistry and introduction to electrodeposition of metals and alloys. Papers relevant to INIS are indexed separately

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

    Science.gov (United States)

    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. Blood glucose meters employing dynamic electrochemistry are stable against hematocrit interference in a laboratory setting.

    Science.gov (United States)

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

    2013-11-01

    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). 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)]. 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%). 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. © 2013 Diabetes Technology Society.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

  19. A review of electrochemistry of relevance to environment-assisted cracking in light water reactors

    International Nuclear Information System (INIS)

    Turnbull, A.; Psaila-Dombrowski, M.

    1992-01-01

    The electrochemistry of relevance to environment-assisted cracking in high temperature, low conductivity water is critically reviewed. The review covers corrosion potential and electrochemical polarisation measurements, thermodynamics, and also experimental measurements and mathematical modelling of the electrochemistry in cracks and crevices. There is a lack of critical data in relation to the electrode kinetics of relevant cathodic reduction reactions, namely H + , H 2 O, O 2 , H 2 O 2 and steady-state anodic reaction data are limited. Transient anodic current measurements, associated with initially film-free metal, have been made for a range of conditions but there is uncertainty regarding the role of fluid flow and transport processes on the current decay characteristics. A number of experimental measurements of potential and pH in crevices and cracks have been made but the experiments are difficult to carry out reliably and hence the range of data of relevance to practical conditions is very limited. Recent developments in mathematical modelling have significantly enhanced the qualitative understanding of the processes controlling the local electrochemistry in cracks and crevices but the reliability of the quantitative predictions is limited by the paucity of reliable input data. (Author)

  20. Electrochemistry of cytochrome P450 17α-hydroxylase/17,20-lyase (P450c17).

    Science.gov (United States)

    Martin, Lisandra L; Kubeil, Clemens; Simonov, Alexandr N; Kuznetsov, Vladimir L; Corbin, C Jo; Auchus, Richard J; Conley, Alan J; Bond, Alan M; Rodgers, Raymond J

    2017-02-05

    Within the superfamily of cytochrome P450 enzymes (P450s), there is a small class which is functionally employed for steroid biosynthesis. The enzymes in this class appear to have a small active site to accommodate the steroid substrates specifically and snuggly, prior to the redox transformation or hydroxylation to form a product. Cytochrome P450c17 is one of these and is also a multi-functional P450, with two activities, the first 17α-hydroxylation of pregnenolone is followed by a subsequent 17,20-lyase transformation to dehydroepiandrosterone (DHEA) as the dominant pathways to cortisol precursors or androgens in humans, respectively. How P450c17 regulates these two redox reactions is of special interest. There is a paucity of direct electrochemical studies on steroidogenic P450s, and in this mini-review we provide an overview of these studies with P450c17. Historical consideration as to the difficulties in obtaining reliable electrochemistry due to issues of handling proteins on an electrode, together with advances in the electrochemical techniques are addressed. Recent work using Fourier transformed alternating current voltammetry is highlighted as this technique can provide both catalytic information simultaneously with the underlying redox transfer with the P450 haem. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  1. Mono and dinuclear rhodium, iridium and ruthenium complexes containing chelating 2,2´-bipyrimidine ligands: Synthesis, molecular structure, electrochemistry and catalytic properties

    Czech Academy of Sciences Publication Activity Database

    Govindaswamy, P.; Canivet, J.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

    2007-01-01

    Roč. 692, č. 17 (2007), s. 3664-3675 ISSN 0022-328X R&D Projects: GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : arene ligands * electrochemistry * dinuclear complexes * transfer hydrogenation Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

  2. Application of nanodisc technology for direct electrochemical investigation of plant cytochrome P450s and their NADPH P450 oxidoreductase

    DEFF Research Database (Denmark)

    Bavishi, Krutika; Laursen, Tomas; Martinez, Karen Laurence

    2016-01-01

    Direct electrochemistry of cytochrome P450 containing systems has primarily focused on investigating enzymes from microbes and animals for bio-sensing applications. Plant P450s receive electrons from NADPH P450 oxidoreductase (POR) to orchestrate the bio-synthesis of a plethora of commercially...... was electro-catalytically active while the P450s generated hydrogen peroxide (H2O2). These nanodisc-based investigations lay the prospects and guidelines for construction of a simplified platform to perform mediator-free, direct electrochemistry of non-engineered cytochromes P450 under native-like conditions...

  3. Aerodynamic and thermal studies of cans of gas cooled fuel elements; Etudes aerodynamiques et thermiques de gaines d'elements combustibles refroidis par gaz

    Energy Technology Data Exchange (ETDEWEB)

    Gelin, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Milliat, J P [Electricite de France (EDF), 75 - Paris (France)

    1964-07-01

    Research on clusters was undertaken at the CEA in 1959, while studies on herring-bone cans were developed at the EDF Laboratory at Chatou and the CEA laboratory at Saclay at the end of 1959. In 1962, a general study on corrugations was begun at the Saclay Laboratory with a view to improving the clusters, and continued later in both laboratories relative to the internal cooling of annular fuel elements. As these studies progressed, trial facilities were extended while experimental methods have improved constantly. At the present time, both laboratories, working in complete collaboration, have powerful means at their disposal. Work on the clusters has been concerned chiefly with pressure losses due to the assembly parts, and with the temperature variations around the elements of the cluster. In this way, we have been able to determine satisfactorily the hot points of the can, the deformations of the rods and the conditions of stability of these deformations. In the case of the herring-bone cans, studies have been directed to the evolution of performances as a function of the geometric parameters on the one hand, and to the special aerodynamic and thermal features caused by the fins and by interruptions of cartridge on the other hand. These studies have led to a very thorough knowledge of the cartridges chosen for the reactors EDF 2 and EDF 3, and now open up very hopeful prospects for future reactors, particularly those fitted with annular elements; among the alternatives suitable for the inner surface of the annular element can, corrugations and longitudinal fins have been fairly extensively tested over a wide range of Reynolds number. (authors) [French] Les etudes de grappes ont ete entreprises au C.E.A. en 1959, tandis que les etudes de gaines a chevrons se sont developpees au Laboratoire de Chatou de l'EDF et au Laboratoire de Saclay du C.E.A. a la fin de l'annee 1959. En 1962, une etude generale sur les corrugations a ete commencee au Laboratoire de Saclay pour

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  6. An experimental applications of impedance measurements by spectral analysis to electrochemistry and corrosion

    International Nuclear Information System (INIS)

    Castro, E.B.; Vilche, J.R.; Milocco, R.H.

    1984-01-01

    An impedance measurement system based on the spectral analysis of excitation and response signals was implemented using a pseudo-random binary sequence in the generation of the electrical perturbation signal. The spectral density functions were estimated through finite Fourier transforms of the original time history records by fast computation of Fourier series. Experimental results obtained using the FFT algorithm in the developed impedance measurement system which covers a wide frequency range, 10 KHz >= f >= 1 mHz, are given both for dummy cells representing conventional electric circuits in electrochemistry and corrosion systems and for the Fe/acidic chloride solution interfaces under different polarization conditions. (C.L.B.) [pt

  7. Functionalizing Arrays of Transferred Monolayer Graphene on Insulating Surfaces by Bipolar Electrochemistry

    DEFF Research Database (Denmark)

    Koefoed, Line; Pedersen, Emil Bjerglund; Thyssen, Lena

    2016-01-01

    Development of versatile methods for graphene functionalization is necessary before use in applications such as composites or as catalyst support. In this study, bipolar electrochemistry is used as a wireless functionalization method to graft 4-bromobenzenediazonium on large (10 × 10 mm2) monolayer...... graphene sheets supported on SiO2. Using this technique, transferred graphene can be electrochemically functionalized without the need of a metal support or the deposition of physical contacts. X-ray photoelectron spectroscopy and Raman spectroscopy are used to map the chemical changes and modifications...

  8. A short introduction to digital simulations in electrochemistry: simulating the Cottrell experiment in NI LabVIEW

    Directory of Open Access Journals (Sweden)

    Soma Vesztergom

    2018-05-01

    Full Text Available A brief introduction to the use of digital simulations in electrochemistry is given by a detailed description of the simulation of Cottrell’s experiment in the LabVIEW programming language. A step-by-step approach is followed and different simulation techniques (explicit and implicit Euler, Runge–Kutta and Crank–Nicolson methods are applied. The applied techniques are introduced and discussed on the basis of Padé approximants. The paper might be found useful by undergraduate and graduate students familiarizing themselves with the digital simulation of electrochemical problems, as well as by university lecturers involved with the teaching of theoretical electrochemistry.

  9. Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems

    Energy Technology Data Exchange (ETDEWEB)

    Lines, Amanda M. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Adami, Susan R. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Casella, Amanda J. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Sinkov, Sergey I. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Lumetta, Gregg J. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352; Bryan, Samuel A. [Nuclear Chemistry and Engineering, Pacific Northwest National Laboratory, Richland WA 99352

    2017-09-20

    The solution chemistry of Pu in nitric acid is explored via electrochemistry and spectroelectrochemistry. By utilizing and comparing these techniques, an improved understanding of Pu behavior and its dependence on nitric acid concentration can be achieved. Here the Pu (III/IV) couple is characterized using cyclic voltammetry, square wave voltammetry, and a spectroelectrochemical Nernst step. Results indicate the formal reduction potential of the couple shifts negative with increasing acid concentration and reversible electrochemistry is no longer attainable above 6 M HNO3. Spectroelectrochemistry is also used to explore the irreversible oxidation of Pu(IV) to Pu(VI) and shine light on the mechanism and acid dependence of the redox reaction.

  10. Ultrahigh-vacuum in situ electrochemistry with solid polymer electrolyte and x-ray photoelectron spectroscopy studies of polypyrrole

    International Nuclear Information System (INIS)

    Skotheim, T.A.; Florit, M.I.; Melo, A.; O'Grady, W.E.

    1984-01-01

    A new in situ combined electrochemistry and x-ray-photoelectron-spectroscopy (XPS) technique using solid polymer electrolytes has been used to characterize electrically conducting films of polypyrrole perchlorate. The technique allows in situ electrochemical oxidation and reduction (doping and undoping) in ultrahigh vacuum and the simultaneous study of the polymer with XPS as a function of its electrochemical potential. We demonstrate that some anion species interact strongly electrostatically with the nitrogen heteroatoms. We also show conclusively that the electrochemistry of polypyrrole is highly irreversible

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  13. Treatment of effluent at the Saclay Centre d'Etudes Nucleaires (1960); Le traitement des effluents du Centre d'Etudes Nucleaires de Saclay (1960)

    Energy Technology Data Exchange (ETDEWEB)

    Wormser, G [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    The Centre d'Etudes Nucleaires at Saclay possesses several installations from which liquid radioactive effluent is rejected, and it has thus been found necessary to construct a station for the purification of radioactive liquids and to settle various chemical, analytical and technological problems. This report describes, in the following order: - the disposal possibilities at the Centre d'Etudes Nucleaires, Saclay, - the effluents produced at the centre, - the set-up for collecting effluent, - treatment of the effluent, - results of these treatments. (author) [French] La presence, au Centre d'Etudes Nucleaires de Saclay, de plusieurs installations susceptibles de rejeter des effluents liquides radioactifs a necessite la construction d'une station d'epuration d'eaux radioactives et la mise au point de differents problemes chimiques, analytiques et technologiques. Dans ce rapport, nous exposerons successivement: - les possibilites de rejet du Centre d'Etudes Nucleaires de Saclay, - les effluents du centre, - le dispositif de collecte des effluents, - le traitement de ces effluents, - les resultats de ces traitements. (auteur)

  14. Proton Conducting Fuel Cells where Electrochemistry Meets Material Science

    DEFF Research Database (Denmark)

    Li, Qingfeng

    Fuel cells are electrochemical devices which directly convert the chemical energy of fuels into electrical energy. They are featured of high energy conversion efficiency and minimized pollutant emission. Proton conducting electrolytes are primarily used as separator materials for low and intermed...... science point of view including novel proton conducting materials and non-precious metal catalysts. The discussion will be made with highlights of DTU´s recent research and of course addressing a diverse technical audience.......Fuel cells are electrochemical devices which directly convert the chemical energy of fuels into electrical energy. They are featured of high energy conversion efficiency and minimized pollutant emission. Proton conducting electrolytes are primarily used as separator materials for low...... followed by a review of the state-of-the-art in terms of performance, lifetime and cost. Technically faced challenges are then outlined on a system level and traced back to fundamental issues of the proton conducting mechanisms and materials. Perspectives and future research are sketched from a materials...

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

    Science.gov (United States)

    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.

  16. Etudes sur le Portugal au Temps de l'Humanisme

    Directory of Open Access Journals (Sweden)

    J. Cruz Costa

    1953-06-01

    Full Text Available BATAILLON (Marcel. — Etudes sur le Portugal au Temps de l'Humanisme.  Acta Universitatis Conimbrigencis, 1952, 309 pp. (Primeiro Parágrafo do Artigo O Prof. Marcel Bataillon, erudito dos mais inteligentes da França atual, autor de uma obra que é hoje impr:scindível para quem pretenda estudar o humanismo renascentista na Espanha ou em Portugal, diríamos melhor, talvez: para quem pretenda estudar o Humanismo e a Renascença, — acaba de publicar, na coleção Acta Universitatis Conimbrigencis, êste volume no qual reune alguns trabalhos da mais alta importância para o conhecimento de muitos aspectos da vida espiritual portuguêsa do século XVI.

  17. ETUDE DE LA DISTRIBUTION DES CATIONS ECHANGEABLES

    African Journals Online (AJOL)

    SEI Joseph

    D'autre part, à cause de la corrélation directe entre l'étendue des inondations et les quantités de poissons et de pâturages fournies par la plaine, il y a eu dégradation des ... aux changements climatiques en zone sahélienne du Cameroun. Un des objectifs de notre étude était de préciser le comportement des agriculteurs ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Eshghinejad, Ahmadreza; Nasr Esfahani, Ehsan; Wang, Peiqi; Li, Jiangyu, E-mail: jjli@uw.edu [Department of Mechanical Engineering, University of Washington, Seattle, Washington 98195 (United States); Xie, Shuhong [Key Laboratory of Low Dimensional Materials and Application Technology of Ministry of Education, School of Materials Science and Engineering, Xiangtan University, Xiangtan 411105, Hunan (China); Shenzhen Key Laboratory of Nanobiomechanics, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, Guangdong (China); Geary, Timothy C.; Adler, Stuart B. [Department of Chemical Engineering, University of Washington, Seattle, Washington 98195 (United States)

    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.

  19. On-line probe for fast electrochemistry/electrospray mass spectrometry. Investigation of polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Xu, X; Lu, W; Cole, R B

    1996-12-01

    A newly invented probe accessory for fast electrochemistry/electrospray mass spectrometry (EC/ESMS) is presented and evaluated. The device features a low-volume, three-electrode electrochemical cell which has been designed with a minimum distance between the working electrode and the "Taylor cone" inherent to the electrospray process. This configuration limits the time between electrochemical generation of ions and mass spectrometric analysis to an absolute minimum. A fused-silica layer insulates the microcylinder working electrode from the sample solution until immediately prior to the electrospray region, postponing electrode processes until the last moment. The same fused-silica layer insulates the working electrode from the surrounding auxiliary electrode, a stainless steel capillary that also serves as the electrospray capillary. The performance and capabilities of the novel electrochemistry/electrospray mass spectrometry system have been evaluated using polycyclic aromatic hydrocarbons (PAHs) as test analytes. In the positive ion EC/ESMS mode, oxidized forms (one-electron removal) of PAHs are produced in high yield. The ability to analyze reaction products appearing subsequent to the initial oxidation is also demonstrated.

  20. Electrochemistry-High Resolution Mass Spectrometry to Study Oxidation Products of Trimethoprim

    Directory of Open Access Journals (Sweden)

    Marc-André Lecours

    2018-01-01

    Full Text Available The study of the fate of emerging organic contaminants (EOCs, especially the identification of transformation products, after water treatment or in the aquatic environment, is a topic of growing interest. In recent years, electrochemistry coupled to mass spectrometry has attracted a lot of attention as an alternative technique to investigate oxidation metabolites of organic compounds. The present study used different electrochemical approaches, such as cyclic voltammetry, electrolysis, electro-assisted Fenton reaction coupled offline to high resolution mass spectrometry and thin-layer flow cell coupled online to high resolution mass spectrometry, to study oxidation products of the anti-infective trimethoprim, a contaminant of emerging concern frequently reported in wastewaters and surface waters. Results showed that mono- and di-hydroxylated derivatives of trimethoprim were generated in electrochemically and possibly tri-hydroxylated derivatives as well. Those compounds have been previously reported as mammalian and bacterial metabolites as well as transformation products of advance oxidation processes applied to waters containing trimethoprim. Therefore, this study confirmed that electrochemical techniques are relevant not only to mimic specific biotransformation reactions of organic contaminants, as it has been suggested previously, but also to study the oxidation reactions of organic contaminants of interest in water treatment. The key role that redox reactions play in the environment make electrochemistry-high resolution mass spectrometry a sensitive and simple technique to improve our understanding of the fate of organic contaminants in the environment.

  1. Corrosion of structural materials and electrochemistry in high temperature water of nuclear power systems

    International Nuclear Information System (INIS)

    Uchida, Shunsuke

    2014-01-01

    The latest experiences with corrosion in the cooling systems of nuclear power plants are reviewed. High temperature cooling water causes corrosion of structural materials, which often leads to adverse effects in the plants, e.g., generating defects in materials of major components and fuel claddings, increasing shutdown radiation and increasing the volume of radwaste sources. Corrosion behaviors are much affected by water qualities and differ according to the values of water qualities and the materials themselves. In order to establish reliable operation, each plant requires its own unique optimal water chemistry control based on careful consideration of its system, materials and operational history. Electrochemistry is one of key issues that determine corrosion related problems but it is not the only issue. Most phenomena for corrosion related problems, e.g., flow-accelerated corrosion (FAC), intergranular stress corrosion cracking (IGSCC), primary water stress corrosion cracking (PWSCC) and thinning of fuel cladding materials, can be understood based on an electrochemical index, e.g., electrochemical corrosion potential (ECP), conductivities and pH. The most important electrochemical index, ECP, can be measured at elevated temperature and applied to in situ sensors of corrosion conditions to detect anomalous conditions of structural materials at their very early stages. In the paper, theoretical models based on electrochemistry to estimate wall thinning rate of carbon steel piping due to flow-accelerated corrosion and corrosive conditions determining IGSCC crack initiation and growth rate are introduced. (author)

  2. Understanding oxygen electrochemistry in aprotic LiO2 batteries

    Directory of Open Access Journals (Sweden)

    Liang Wang

    2017-07-01

    Full Text Available In the past decade, the aprotic lithium–oxygen (LiO2 battery has generated a great deal of interest because theoretically it can store more energy than today's lithium-ion batteries. Although considerable research efforts have been devoted to the R&D of this potentially disruptive technology, many scientific and engineering obstacles still remain to be addressed before a practical device could be realized. In this review, we summarize recent advances in the fundamental understanding of the O2 electrochemistry in LiO2 batteries, including the O2 reduction to Li2O2 on discharge and the reverse Li2O2 oxidation on recharge and factors that exert strong influences on the redox of O2/Li2O2. In addition, challenges and perspectives are also provided for the future study of LiO2 batteries. Keywords: Lithium–oxygen battery, Oxygen electrochemistry, Mechanism

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Wigger, Tina; Seidel, Albrecht; Karst, Uwe

    2017-06-01

    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/H 2 , 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. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Metallurgical electrochemistry: the interface between materials science and molten salt chemistry

    International Nuclear Information System (INIS)

    Sadoway, D.R.

    1991-01-01

    Even though molten salt electrolysis finds application in the primary extraction of metals (electrowinning), the purification and recycling of metals (electrorefining), and in the formation of metal coatings (electroplating), the technology remains in many respects underexploited. Electrolysis in molten salts as well as other nonaqueous media has enormous potential for materials processing. First, owing to the special attributes of nonaqueous electrolytes electrochemical processing in these media has an important role to play in the generation of advanced materials, i.e., materials with specialized chemistries or tailored microstructures (electrosynthesis). Secondly, as environmental quality standards rise beyond the capabilities of classical metals extraction technologies to comply, molten salt electrolysis may prove to be the only acceptable route from ore to metal. Growing public awareness of pollution from the metals industry could stimulate a renaissance in molten salt electrochemistry. Challenges facing metallurgical electrochemistry as relates to the environment fall into two categories: (1) improving existing electrochemical technology, and (2) developing clean electrochemical technology to displace current nonelectrochemical technology. In both instances success hinges upon the discovery of advanced materials and the ecologically sound extraction of metals, the close coupling between materials science and molten salt chemistry is manifest. (author) 6 refs

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

    Science.gov (United States)

    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.

  7. The electrochemistry of IGSCC mitigation in BWR coolant circuits

    International Nuclear Information System (INIS)

    Macdonald, D.D.

    2002-01-01

    A brief review is presented of the electrochemical mitigation of IGSCC in water-cooled reactor heat transport circuit structural materials. Electrochemical control and mitigation is possible, because of the existence of a critical potential for IGSCC and by the feasibility of modifying the environment to displace the corrosion potential (ECP) to a value that is more negative than the critical value. However, even in cases where the ECP cannot be displaced sufficiently in the negative direction to become more negative than the critical potential, considerable advantage is accrued, because of the roughly exponential dependence of crack growth rate on potential. The most important parameters in affecting electrochemical control over the ECP and crack growth rate are the kinetic parameters (exchange current densities and Tafel constants) for the redox reactions involving the principal radiolysis products of water (O 2 , H 2 , H 2 O 2 ), external solution composition (concentrations of O 2 , H 2 O 2 , and H 2 ), flow velocity, and the conductivity of the bulk environment. The kinetic parameters for the redox reactions essentially determine the charge transfer impedance of the steel surface, which is shown to be one of the key parameters in affecting the magnitude of the coupling current and hence the crack growth rate. The exchange current densities, in particular, are amenable to control by catalysis or inhibition, with the result that surface modification techniques are highly effective in controlling and mitigating IGSCC in reactor coolant circuit materials. (authors)

  8. The electrochemistry of IGSCC mitigation in BWR coolant circuits

    Energy Technology Data Exchange (ETDEWEB)

    Macdonald, D.D. [Center for Electrochemical Science and Technology, The Pennsylvania State Univ., University Park, PA (United States)

    2002-07-01

    A brief review is presented of the electrochemical mitigation of IGSCC in water-cooled reactor heat transport circuit structural materials. Electrochemical control and mitigation is possible, because of the existence of a critical potential for IGSCC and by the feasibility of modifying the environment to displace the corrosion potential (ECP) to a value that is more negative than the critical value. However, even in cases where the ECP cannot be displaced sufficiently in the negative direction to become more negative than the critical potential, considerable advantage is accrued, because of the roughly exponential dependence of crack growth rate on potential. The most important parameters in affecting electrochemical control over the ECP and crack growth rate are the kinetic parameters (exchange current densities and Tafel constants) for the redox reactions involving the principal radiolysis products of water (O{sub 2}, H{sub 2}, H{sub 2}O{sub 2}), external solution composition (concentrations of O{sub 2}, H{sub 2}O{sub 2}, and H{sub 2}), flow velocity, and the conductivity of the bulk environment. The kinetic parameters for the redox reactions essentially determine the charge transfer impedance of the steel surface, which is shown to be one of the key parameters in affecting the magnitude of the coupling current and hence the crack growth rate. The exchange current densities, in particular, are amenable to control by catalysis or inhibition, with the result that surface modification techniques are highly effective in controlling and mitigating IGSCC in reactor coolant circuit materials. (authors)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  11. In situ generation of copper cations and complexation with tebuconazole in a hyphenation of electrochemistry with mass spectrometry

    Czech Academy of Sciences Publication Activity Database

    Jaklová Dytrtová, Jana; Jakl, M.; Schröder, Detlef; Norková, Renáta

    2013-01-01

    Roč. 338, 15 MAR (2013), s. 45-49 ISSN 1387-3806 R&D Projects: GA ČR GP13-21409P Institutional support: RVO:61388963 Keywords : electrochemical ion generation * ESI-MS * coupling * fungicide * tebuconazole * soil solution Subject RIV: CG - Electrochemistry Impact factor: 2.227, year: 2013

  12. Structural investigation of oxovanadium(IV) Schiff base complexes: X-ray crystallography, electrochemistry and kinetic of thermal decomposition

    Czech Academy of Sciences Publication Activity Database

    Asadi, M.; Asadi, Z.; Savaripoor, N.; Dušek, Michal; Eigner, Václav; Shorkaei, M.R.; Sedaghat, M.

    2015-01-01

    Roč. 136, Feb (2015), 625-634 ISSN 1386-1425 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : Oxovanadium(IV) complexes * Schiff base * Kinetic s of thermal decomposition * Electrochemistry Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.653, year: 2015

  13. A computationally efficient implementation of a full and reduced-order electrochemistry-based model for Li-Ion batteries

    NARCIS (Netherlands)

    Xia, L.; Najafi, E.; Li, Z.; Bergveld, H.J.; Donkers, M.C.F.

    2017-01-01

    Lithium-ion batteries are commonly employed in various applications owing to high energy density and long service life. Lithium-ion battery models are used for analysing batteries and enabling power control in applications. The Doyle-Fuller-Newman (DFN) model is a popular electrochemistry-based

  14. Surfactant-Templated TiO.sub.2./sub. (Anatase): Characteristic Features of Lithium Insertion Electrochemistry in Organized Nanostructures

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav; Rathouský, Jiří; Grätzel, M.; Shklover, V.; Zukal, Arnošt

    2000-01-01

    Roč. 104, č. 50 (2000), s. 12012-12020 ISSN 1089-5647 R&D Projects: GA AV ČR IAA4040804; GA MŠk OC D14.10; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4040901 Subject RIV: CG - Electrochemistry Impact factor: 3.386, year: 2000

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

    Science.gov (United States)

    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…

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

    Science.gov (United States)

    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…

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

    Science.gov (United States)

    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,…

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

    Science.gov (United States)

    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,…

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

    Science.gov (United States)

    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…

  20. Topic-Specific Pedagogical Content Knowledge (TSPCK) in Redox and Electrochemistry of Experienced Teachers

    Science.gov (United States)

    O'Brien, Stephanie

    Topic specific pedagogical content knowledge (TSPCK) is the basis by which knowledge of subject matter of a particular topic is conveyed to students. This includes students' prior knowledge, curricular saliency, what makes a topic easy or difficult to teach, representations, and teaching strategies. The goal of this study is to assess the pedagogical content knowledge of chemistry teachers in a professional learning community in the areas of redox and electrochemistry, as this has been regarded in previous literature as conceptually challenging for students to learn. By acquiring information regarding the PCK development of experienced chemistry teachers, the education and practice of all science teachers can be advanced. This study builds upon previous research that developed validated instruments to evaluate TSPCK. The research questions sought to determine which components of TSPCK were evidenced by the instructional design decisions teachers made, what shared patterns and trends were evident, and how TSPCK related to student learning outcomes. To answer the research questions subjects completed a background questionnaire, a TSPCK assessment, and interview tasks to elicit information about pedagogical decision making and processes that influenced student learning in their classrooms. The TSPCK exam and interview responses were coded to align with thematic constructs. To determine the effect of TSPCK on student learning gains, pre/post-assessment data on redox and electrochemistry were compared to teachers' TSPCK. The chemistry teachers displayed varying levels of TSPCK in redox and electrochemistry, as evidenced by their knowledge of student learning obstacles, curricular saliency, and teaching methodologies. There was evidence of experienced teachers lacking in certain areas of TSPCK, such as the ability to identify student misconceptions, suggesting the need for programmatic improvements in pre-service and in-service training to address the needs of current

  1. Contribution to the study of several chemical hazards in the Centre d'Etudes Nucleaires of Fontenay-aux-Roses; Contribution a l'etude de quelques nuisances chimiques au centre d'etudes nucleaires de Fontenay-aux-Roses

    Energy Technology Data Exchange (ETDEWEB)

    Megemont, C; Grau, C [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1968-10-01

    From the checking of 2750 index cards of hazards, the study relates the distribution of the chemical hazards in the Centre d'Etudes Nucleaires of Fontenay-aux-Roses. Those concerning the greatest number of agents in the Centre are classified according to the categories corresponding to the different conditions of working. Thus, the most important are put forward. Then, the authors rapidly make a review of hazards which may have some special interest because they appear more specific of the nuclear energy or because they are the most frequently noted on the index cards of hazards. The case of the tributylphosphate is studied more precisely. (authors) [French] A partir de l'examen de 2750 fiches de nuisances, l'etude porte sur la repartition des nuisances chimiques au Centre d'Etudes Nucleaires de Fontenay-aux-Roses. Celles qui concernent le plus grand nombre d'agents du Centre sont classees selon les categories correspondant aux differentes conditions de travail. Les plus importantes d'entre elles sont ainsi mises en evidence. | Les auteurs passent ensuite en revue, rapidement, les nuisances qui peuvent presenter un interet particulier soit parce qu'elles semblent plus specifiques de l'Energie Nucleaire, soit parce qu'on les rencontre le plus frequemment sur les fiches de nuisances. Le cas du tributylphosphate est envisage de facon plus detaillee. (auteurs)

  2. JPRS Report, Science & Technology, Japan, International Society of Electrochemistry Meeting (40th) Held in Kyoto on 17-22 Sep 89

    National Research Council Canada - National Science Library

    1990-01-01

    Selected "extended abstracts" presented at the 40th International Society of Electrochemistry Meeting held 17-22 Sep 89 in Kyoto, sponsored by the International Union of Pure and Applied Chemistry (IUPAC...

  3. Electrochemistry in light water reactors reference electrodes, measurement, corrosion and tribocorrosion issues

    CERN Document Server

    Bosch, R -W; Celis, Jean-Pierre

    2007-01-01

    There has long been a need for effective methods of measuring corrosion within light water nuclear reactors. This important volume discusses key issues surrounding the development of high temperature reference electrodes and other electrochemical techniques. The book is divided into three parts with part one reviewing the latest developments in the use of reference electrode technology in both pressurised water and boiling water reactors. Parts two and three cover different types of corrosion and tribocorrosion and ways they can be measured using such techniques as electrochemical impedance spectroscopy. Topics covered across the book include in-pile testing, modelling techniques and the tribocorrosion behaviour of stainless steel under reactor conditions. Electrochemistry in light water reactors is a valuable reference for all those concerned with corrosion problems in this key technology for the power industry. Discusses key issues surrounding the development of high temperature reference eletrodes A valuab...

  4. Boundary asymptotics for a non-neutral electrochemistry model with small Debye length

    Science.gov (United States)

    Lee, Chiun-Chang; Ryham, Rolf J.

    2018-04-01

    This article addresses the boundary asymptotics of the electrostatic potential in non-neutral electrochemistry models with small Debye length in bounded domains. Under standard physical assumptions motivated by non-electroneutral phenomena in oxidation-reduction reactions, we show that the electrostatic potential asymptotically blows up at boundary points with respect to the bulk reference potential as the scaled Debye length tends to zero. The analysis gives a lower bound for the blow-up rate with respect to the model parameters. Moreover, the maximum potential difference over any compact subset of the physical domain vanishes exponentially in the zero-Debye-length limit. The results mathematically confirm the physical description that electrolyte solutions are electrically neutral in the bulk and are strongly electrically non-neutral near charged surfaces.

  5. Study on tribological and electrochemistry properties of metal materials in H2O2 solutions

    Science.gov (United States)

    Yuan, Chengqing; Yu, Li; Li, Jian; Yan, Xinping

    2012-03-01

    Hydrogen peroxide (H2O2) is a kind of ideal green propellant. It is crucial to study the wear behavior and failure modes of the metal materials under the strong oxidizing environment of H2O2. This study aims to investigate the wear of rubbing pairs of 2Cr13 stainless steel against 1045 metal in H2O2 solutions, which has a great effect on wear, the decomposition and damage mechanism of materials. The comparison analysis of the friction coefficients, wear mass loss, worn surface topographies and current densities was conducted under different concentrations of H2O2 solutions. There were significant differences in the tribological and electrochemistry properties of the rubbing pairs in different H2O2 solutions.

  6. Electrochemistry and capillary condensation theory reveal the mechanism of corrosion in dense porous media.

    Science.gov (United States)

    Stefanoni, Matteo; Angst, Ueli M; Elsener, Bernhard

    2018-05-09

    Corrosion in carbonated concrete is an example of corrosion in dense porous media of tremendous socio-economic and scientific relevance. The widespread research endeavors to develop novel, environmentally friendly cements raise questions regarding their ability to protect the embedded steel from corrosion. Here, we propose a fundamentally new approach to explain the scientific mechanism of corrosion kinetics in dense porous media. The main strength of our model lies in its simplicity and in combining the capillary condensation theory with electrochemistry. This reveals that capillary condensation in the pore structure defines the electrochemically active steel surface, whose variability upon changes in exposure relative humidity is accountable for the wide variability in measured corrosion rates. We performed experiments that quantify this effect and find good agreement with the theory. Our findings are essential to devise predictive models for the corrosion performance, needed to guarantee the safety and sustainability of traditional and future cements.

  7. Electrochemistry as a Tool for Study, Delvelopment and Promotion of Catalytic Reactions

    DEFF Research Database (Denmark)

    Petrushina, Irina

    of Fermi level by electrochemical production of promoters, reducing or oxidizing current carriers of the catalyst support (O2-, H+, Na+). This type1 was abbreviated as EEPP. In Capters 4-7, the results of my research are given as examples of use of electrochemistry as a tool for study, promotion...... be measured and changed by polarization in electrochemical experiment. In Chapter 3 the nature of the electrochemical heterogeneous catalytic reactions is dicussed, including the new theory of electrochemical promotion. This theory is based on electrochemical change of the Fermi level of the catalyst. It also...... states that that there are two types of electrochemical promotion: First type is based on change of the Fermi level through the charge of the electric double layer (EDL) between catalyst and its support without electrochemical reaction. This effect was abbreviated as EDLE. Second type is based on change...

  8. Spectroscopy and electrochemistry of U(IV/III) in basic AlCl3-EMIC

    International Nuclear Information System (INIS)

    Anderson, C.J.; Deakin, M.R.; Choppin, G.R.; Heerman, L.; D'Olieslager, W.; Pruett, D.J.

    1990-01-01

    The electrochemistry of U(IV) has been investigated in the solvent AlCl 3 -1-ethyl-3-methyl imidazolium chloride (EMIC), a room temperature ionic liquid. In basic solutions ( 3 ) the reduction of U(IV) to U(III) on glassy carbon electrodes is reversible. Spectroscopic data as well as measurements of the formal potential for U(IV)/U(III) as a function of the basic melt composition indicate that U(IV) and U(III) are both hexachloro anions. Diffusion coefficients for these species have been measured by two methods. The values are comparable to those of transition metal hexachloro complexes in the same solvent, supporting the assignment of UCl 6 2- and UCl 6 3-

  9. Electrochemistry of chromium subgroup transition metal ions in an ambient temperature chloroaluminate molten salt

    International Nuclear Information System (INIS)

    Scheffler, T.B.

    1984-01-01

    The electrochemistry of several chromium subgroup transition metal solutes was studied in the basic AlCl 3 -1-methyl-3-ethylimidazolium chloride (MEIC) ionic liquid at 40.0 0 C by using stationary and rotating disk electrode voltametry, chronoamperometry, coulometry, and UV-vis spectrophotometry. Chromium(III) was present in the melt as the chloro complex [CrCl 6 ] 3- . This complex underwent as essentially irreversible reduction, apparently as a result of slow charge-transfer, to a chromium(II) species at ca. -1.08 V versus an aluminum wire immersed in 66.7 mol % melt. Similar investigations of molybdenum and tungsten were also conducted. Mechanisms are proposed to account for the results

  10. Nanopore Electrochemistry: A Nexus for Molecular Control of Electron Transfer Reactions

    Science.gov (United States)

    2018-01-01

    Pore-based structures occur widely in living organisms. Ion channels embedded in cell membranes, for example, provide pathways, where electron and proton transfer are coupled to the exchange of vital molecules. Learning from mother nature, a recent surge in activity has focused on artificial nanopore architectures to effect electrochemical transformations not accessible in larger structures. Here, we highlight these exciting advances. Starting with a brief overview of nanopore electrodes, including the early history and development of nanopore sensing based on nanopore-confined electrochemistry, we address the core concepts and special characteristics of nanopores in electron transfer. We describe nanopore-based electrochemical sensing and processing, discuss performance limits and challenges, and conclude with an outlook for next-generation nanopore electrode sensing platforms and the opportunities they present. PMID:29392173

  11. Nanopore Electrochemistry: A Nexus for Molecular Control of Electron Transfer Reactions

    Directory of Open Access Journals (Sweden)

    Kaiyu Fu

    2018-01-01

    Full Text Available Pore-based structures occur widely in living organisms. Ion channels embedded in cell membranes, for example, provide pathways, where electron and proton transfer are coupled to the exchange of vital molecules. Learning from mother nature, a recent surge in activity has focused on artificial nanopore architectures to effect electrochemical transformations not accessible in larger structures. Here, we highlight these exciting advances. Starting with a brief overview of nanopore electrodes, including the early history and development of nanopore sensing based on nanopore-confined electrochemistry, we address the core concepts and special characteristics of nanopores in electron transfer. We describe nanopore-based electrochemical sensing and processing, discuss performance limits and challenges, and conclude with an outlook for next-generation nanopore electrode sensing platforms and the opportunities they present.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  14. Semiconductor electrochemistry

    National Research Council Canada - National Science Library

    Memming, Rüdiger

    2001-01-01

    ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Energy Levels in Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Density...

  15. Electrochemistry Experiments to Develop Novel Sensors for Real-World Applications

    Directory of Open Access Journals (Sweden)

    Suzanne Lunsford

    2013-08-01

    Full Text Available These novel STEM (Science Technology Engineering and Mathematics Electrochemistry experiments have been designed to increase the integrated science content, pedagogical, and technological knowledge for real-world applications. This study has focused on (1 the fundamental understanding on the relationship of metal oxide films and polymers to electrochemical sensors, and (2 the development of new materials which have great application of electrode materials. Following the inquiry based learning strategy the research students learn to develop and study the electrode surfaces to meet the needs of stability and low detection limits. Recently, new advances in environmental health are revealing the anthropogenic or naturally occurring harmful organic chemicals in sources of water supply expose a great health threat to human and aquatic life. Due to their well-known carcinogenic and lethal properties, the presence of human produced toxic chemicals such as phenol and its derivatives poses a critical threat to human health and aquatic life in such water resources. In order to achieve effective assessment and monitoring of these toxic chemicals there is a need to develop in-situ (electrochemical sensors methods to detect rapidly. Electrochemical sensors have attracted more attention to analytical chemist and electrochemistry engineers due to its simplicity, rapidness and high sensitivity. However, there will be real challenges of achieving successful analysis of chemicals (phenol in the presence of common interferences in water resources, which will be discussed regarding the students challenging learning experiences in developing an electrochemical sensor. The electrochemical sensor developed (TiO2 , ZrO2 or sol-gel mixture TiO2/ZrO2 will be illustrated and the successes will be shown by cyclic voltammetry data in detection of 1,2-dihydroxybenzenes (catechol, dopamine and phenol.

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

    Science.gov (United States)

    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.

  17. Etude de la qualité physico-chimique et biologique des eaux du ...

    African Journals Online (AJOL)

    Etude de la qualité physico-chimique et biologique des eaux du fleuve Niger à Niamey. ... le récepteur principal des rejets d'eaux usées de la ville de Niamey, capital du ... La description de ces taxons montre une variation de la structure des ...

  18. English Department Reforms at the Hautes Etudes Commerciales: Entering the Nineties.

    Science.gov (United States)

    Shanahan, Daniel

    1993-01-01

    Discusses the reforms made in the fall of 1990 in the English department at the Ecole Hautes Etudes Commerciales (Paris, France), which were based on the basis of a combination of literature-culture and second- and foreign-language acquisition pedagogical biases. (four references) (VWL)

  19. Contribution a l'etude des plantes alimentaires mineures dans la ...

    African Journals Online (AJOL)

    Contribution a l'etude des plantes alimentaires mineures dans la prefecture de Dankpen (Togo). AB Kebenzikato, S Akpavi, K Batawila, K Wala, M Dourma, K Kossi-Titrikou, KS Amouzou, I Butare, H Dantsey-Barry, K Akpagana ...

  20. 152 Etude de cas sur l'impact des amendements organiques vis-à ...

    African Journals Online (AJOL)

    john mukalay

    Etude de cas sur l'impact des amendements organiques vis-à-vis de la salinité en culture de bananier. Michel Mazinga KWEY1, Séverin Kalala BANZE2 et John Banza MUKALAY2*. 1Laboratoire des cultures in vitro, Département de phytotechnie, Faculté des sciences agronomiques,. Université de Lubumbashi, BP 1825, ...

  1. 186 Etude théorique du transport électronique par la simulation ...

    African Journals Online (AJOL)

    youness

    Choukria SAYAH et al. 186. Etude théorique du ... For that we carried out the microscopic simulations, based on the Monte. Carlo method. ... intervalles, piezoelectric as well as the interactions of alloy and on ionized impurities. ..... SAYA et al. 198. [5] - R. W. Hockney, J. W. Eastwood, "Computer simulation using particles",.

  2. Etude comparative de la flore aux abords des cours d'eau dans les ...

    African Journals Online (AJOL)

    Etude comparative de la flore aux abords des cours d'eau dans les zones hypo et hyper endémiques d'ulcère de Buruli en Côte d'Ivoire. C. Cisse Boni, E. Ehouman, D. Soro, M.W. Kone, A. Bakayoko, F. Dembele, K. Bauthire, M Dosso ...

  3. Alecto 2 - interaction studies; Alecto 2 - etudes d'interaction

    Energy Technology Data Exchange (ETDEWEB)

    Brunet, J P; Clouet d' Orval, Ch; Mougniot, J C; Penet, F [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1965-07-01

    Weak interactions were experimentally studies with the tank of the critical assembly Alecto II and one, two or three bottles containing solutions of various concentrations. In particular, was studied the validity of certain classical assumptions, shielding effects, screening and semi-reflexion effects, importance of thermal coupling. The method of the 'k{sub eff}, solid angle' is shown to apply to such a system. The determination by divergence and pulsed neutron technique of the reactivity related to a millimeter of solution level affords the obtention of critical heights in terms of reactivity. (authors) [French] Une etude experimentale d'interactions faibles a ete faite entre la cuve de l'experience critique ALECTO II et une, deux ou trois bouteilles contenant des concentrations variees. On etudie, en particulier, la validite de certaines hypotheses classiques, effets d'ombre, d'ecrans, de semi-reflexion, importance du couplage thermique. On montre d'autre part que la methode du 'K{sub eff}, angle solide' peut s'appliquer a un tel systeme. La determination par divergence et neutrons pulses de la reactivite liee au millimetre de solution permet de traduire les hauteurs critiques obtenues, en terme de reactivite. (auteurs)

  4. Baby fission chambers; Etude de chambres a fission miniatures

    Energy Technology Data Exchange (ETDEWEB)

    Guery, U; Tachon, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1957-07-01

    The present report is intended, on the one band, as a study of the main types of fission chambers produced to date, and on the other, to deal more generally with this type of detector. Originally, it was with a view to the charting of neutron scatter in 'Proserpine' that the authors undertook the study of these chambers. During the course of the task, it was considered worth tbe trouble of developing its scope to include a more general application: neutron scatter measurement of various energy neutrons within a reduced volume with slight local disturbance. (author) [French] Le present rapport se propose, d'une part, d'exposer les principales realisations de chambres a fission, d'autre part de faire une mise au point a caractere plus general sur ces detecteurs. Au depart, c'est surtout en vue des mesures de densite neutronique dans 'Proserpine' que les auteurs ont etudie ces chambres; au cours de la mise au point, il a paru interessant de developper leur etude pour des applications plus generales: mesures de densites de neutrons de differentes energies dans un element de volume tres reduit et avec faible perturbation locale. (auteur)

  5. SEPA (Service d'etudes, de Procedes et Analyses)

    International Nuclear Information System (INIS)

    2017-01-01

    The SEPA (Service d'etudes, de Procedes et Analyses), is an engineering department specializing in the analysis and processing of uranium ore. It comes from a long tradition of mining in France that began sixty-five years ago with the French Atomic Energy Commission (CEA) and that has been carried on by COGEMA and then Areva. SEPA brings a combination of experience and excellence to its activities thanks to its multidisciplinary staff (mineralogists, chemists, mechanical engineers, instrumentation specialists...), who come from diverse cultural backgrounds. Today, the SEPA draws on its wealth of know-how and expertise to devise and develop new methods for processing and valorizing ores everywhere in the world. Its mission is to: - Develop and conduct laboratory tests on methods for processing uranium and other valuable elements such as molybdenum, vanadium, rare earths, niobium, tantalum and thorium; - Analyze ores obtained during prospecting at locations all over the world; -Serve as an advisor in the commissioning of Areva industrial units and ore processing plants; -Perform environmental analyses during the full period of mining operations; -Conduct audits and provide advice on processes and analysis methods; -Carry out research and development in all aspects of minerals treatment (including the filing of patents). The SEPA combines experience, skills and a global approach to technologies used in ore processing. Its role is to continually improve the processes for extracting, processing and valorizing ores while protecting the environment

  6. Baby fission chambers; Etude de chambres a fission miniatures

    Energy Technology Data Exchange (ETDEWEB)

    Guery, U.; Tachon, J. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1957-07-01

    The present report is intended, on the one band, as a study of the main types of fission chambers produced to date, and on the other, to deal more generally with this type of detector. Originally, it was with a view to the charting of neutron scatter in 'Proserpine' that the authors undertook the study of these chambers. During the course of the task, it was considered worth tbe trouble of developing its scope to include a more general application: neutron scatter measurement of various energy neutrons within a reduced volume with slight local disturbance. (author) [French] Le present rapport se propose, d'une part, d'exposer les principales realisations de chambres a fission, d'autre part de faire une mise au point a caractere plus general sur ces detecteurs. Au depart, c'est surtout en vue des mesures de densite neutronique dans 'Proserpine' que les auteurs ont etudie ces chambres; au cours de la mise au point, il a paru interessant de developper leur etude pour des applications plus generales: mesures de densites de neutrons de differentes energies dans un element de volume tres reduit et avec faible perturbation locale. (auteur)

  7. Contribution to the study of samarium-151 excited levels; Contribution a l'etude des niveaux excites du samarium-151

    Energy Technology Data Exchange (ETDEWEB)

    Locard, P [Commissariat a l' Energie Atomique, Centre d' Etudes Nucleaires de Grenoble, 38 (France)

    1967-07-01

    The nucleus of {sup 151}Sm, which has 89 neutrons, happens to be on the lower edge of the deformed nuclei of region II. Therefore, the study of its levels is very interesting for the verification of the goodness of the collective models for deformed nuclei when the deformation is small (we introduce these models in the first chapter). {sup 151}Sm has often been studied, but the direct gamma spectrum measured with a lithium drift-germanium detector (chapter 3) shows many high energy transitions which did not appear in the previous level schemes. In order to settle these transitions, we have undertaken gamma-gamma coincidence spectra (as well as sum-coincidence spectra) experiments with a scintillation spectrometer designed in our laboratory (chapter 2). The investigation of the intensities of these coincidences leads us to modify the last proposed level schemes: we suppress the levels at 405,5 and 650 keV, we add levels at 245,6 - 306,6 - 522 - 952 and 962 keV. We have also verified the multipolarities of the main transitions and measured the half-lives of a few levels (chapter 3) (we find a half-life of 1.1 {+-} 0.5 nanosecond for the level at 167,7 keV). In chapter 4, we compare our results to the predictions of the models described in chapter 1. (author) [French] Le noyau de {sup 151}Sm, qui possede 89 neutrons, se trouve a la limite inferieure des noyaux deformes de la region II. L'etude de ses niveaux excites est donc d'un interet tout particulier pour la verification de la validite des differents modeles collectifs pour les noyaux deformes, lorsque la deformation est petite (nous introduisons ces modeles dans un premier chapitre). Le {sup 151}Sm a deja fait l'objet de nombreuses etudes, mais le spectre gamma direct fait avec une jonction de germanium compense au lithium (chapitre 3), nous a montre l'existence d'un grand nombre de transitions de hautes energies qui ne sont pas placees dans les schemas proposes jusqu'a ce jour. Pour preciser la place de ces

  8. An approach to automated chromosome analysis; Etudes pour une methode d'automatisation des analyses chromosomiques

    Energy Technology Data Exchange (ETDEWEB)

    Le Go, Roland

    1972-05-03

    d'une automatisation des differentes etapes de l'analyse chromosomique. Il est divise en trois tomes dont la matiere est decrite ci-apres. Dans le tome 1 est decrite l'etude d'un selecteur automatique de metaphases. Cet appareil doit realiser au cours du scanning d'une preparation, un processus de decision aboutissant a rejeter toutes images ininteressantes et a conserver les images pertinentes (bonnes metaphases). Ce probleme a ete aborde au moyen d'une etude sur ordinateur par un programme de simulation. La realisation de ce programme a permis d'etablir des algorithmes de selection dont la replique pourra etre realisee dans des circuits logiques electroniques. Dans le tome 2 est traite le probleme de l'automatisation de l'etude morphologique des chromosomes presents dans une metaphase. Cette automatisation necessite le traitement des photographies de metaphases par un appareil convertisseur optique-numerique qui extrait l'information-image et la transcrit sous la forme d'un fichier numerique. Ce fichier comporte pour une image de metaphase, environ 200 000 valeurs de gris, codees selon une echelle a 16, 32 ou 64 ni veaux. Ce fichier numerique est traite par un programme de reconnaissance de forme, qui isole les chromosomes et en recherche les traits caracteristiques: sommets de bras et region centromerique, dans le but d'obtenir des mensurations equivalentes aux longueurs des quatre bras. Le tome 3 etudie un programme d'etablissement automatique du caryotype humain, par appariement optimise des chromosomes. Les donnees proviennent de la numerisation directe des longueurs de bras, effectuee au moyen d'un lecteur digital BENSON. Le programme etablit une liste des appariements, un document graphique imprime representant les paires constituees, dans l'espace: longueur - index centromerique; enfin un document graphique obtenu sur traceur BENSON dans lequel l'auteur donne une representation personnelle des chromosomes, sous forme de croix a bras orthogonaux, dont chaque

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

    Science.gov (United States)

    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.

  10. Contribution to the study of the vertical molten zone process (1963); Contribution a l'etude du procede de la zone fondue verticale (1963)

    Energy Technology Data Exchange (ETDEWEB)

    Lenzin, M [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1963-07-01

    Construction and use of several molten zone apparatuses operating either vertically or horizontally. Efficient purification of uranyl nitrate hexahydrate but less successful in the case of other hydrated double salts and of zirconyl chloride in the hydrochloric gel form. Demonstration and study of the dissymmetry in the direction of the transport of the impurity during, the purification by a vertical molten zone process. (author) [French] Construction et utilisation de plusieurs appareils de zone fondue travaillant soit en vertical, soit en horizontal. Purification efficace du nitrate d'uranyle hexahydrate mais peu significative dans le cas des autres couples de sels hydrates et du chlorure de zirconyle a l'etat de gel chlorhydrique. Mise en evidence et etude de la dissymetrie sur le sens de transport de l'impurete au cours de la purification par zone fondue verticale. (auteur)

  11. Anthraquinone as a Redox Label for DNA: Synthesis, Enzymatic Incorporation, and Electrochemistry of Anthraquinone-Modified Nucleosides, Nucleotides, and DNA

    Czech Academy of Sciences Publication Activity Database

    Balintová, Jana; Pohl, Radek; Horáková Brázdilová, Petra; Vidláková, Pavlína; Havran, Luděk; Fojta, Miroslav; Hocek, Michal

    2011-01-01

    Roč. 17, č. 50 (2011), s. 14063-14073 ISSN 0947-6539 R&D Projects: GA MŠk(CZ) LC06035; GA MŠk LC512; GA AV ČR(CZ) IAA400040901 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : anthraquinone * DNA * electrochemistry * nucleosides * oligonucleotides Subject RIV: CC - Organic Chemistry Impact factor: 5.925, year: 2011

  12. Synthesis, Structures, and Electrochemistry of Group 6 Aminocarbenes with a P -Chelating 1''-(Diphenylphosphino)ferrocenyl Substituent

    Czech Academy of Sciences Publication Activity Database

    Meca, L.; Dvořák, D.; Ludvík, Jiří; Císařová, I.; Štěpnička, P.

    2004-01-01

    Roč. 23, č. 10 (2004), s. 2541-2551 ISSN 0276-7333 R&D Projects: GA ČR GA203/04/0487; GA ČR GA203/99/M037; GA ČR GP203/01/P002 Institutional research plan: CEZ:AV0Z4040901 Keywords : synthesis * electrochemistry of group 6 * chelating Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.196, year: 2004

  13. X-ray crystallography, electrochemistry, spectral and thermal analysis of some tetradentate schiff base complexes and formation constant measurements

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Savarypour, N.; Dušek, Michal; Eigner, Václav

    2017-01-01

    Roč. 47, č. 11 (2017), s. 1501-1508 ISSN 2470-1556 R&D Projects: GA ČR(CZ) GA15-12653S Institutional support: RVO:68378271 Keywords : X-ray crystallography * transition metal Schiff base complexes * thermogravimetry * electrochemistry * formation constant measurements Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  16. Uncovering the intrinsic relationship of electrocatalysis and molecular electrochemistry for dissociative electron transfer to polychloroethanes at silver cathode

    International Nuclear Information System (INIS)

    Huang, Binbin; Zhu, Yuanyuan; Li, Jing; Zeng, Guangming; Lei, Chao

    2017-01-01

    Highlights: • Thermodynamics of dissociative electron transfer to C–Cl bonds at Ag are studied. • The catalyzed dissociative electron transfer theory was proposed for the first time. • The adsorption of organic chlorides onto Ag plays a key role for dechlorination. • The catalytic property of Ag is ascribed to the lower of intrinsic barrier energy. • The relationship of electrocatalysis and molecular electrochemistry is indicated. - Abstract: The relationship between electrocatalysis and molecular electrochemistry for the reductive dechlorination of organic chlorides has been a central topic for decades. Herein, we try to reveal the catalytic property of silver electrode by investigating the thermodynamics of dissociative electron transfer (DET) to C–Cl bonds of polychloroethanes (PCAs) on both inert (GC) and catalytic (Ag) electrodes. By extending the “sticky” DET model reported by Savéant, we show that the catalyzed DET model can well describe the activation-driving force relationships for the electrocatalytic dechlorination on Ag, where in addition to the possible ion-dipole interations, the adsorption of chlorinated species onto Ag surface, which is found to play a fundamental role in the electrocatalysis process in this study, is introduced in the new developed DET model. In this work, we firstly report that the catalytic property of Ag electrode characterizing with drastically postive shift of reduction potential is ascribed to the lower of intrinsic barrier free energy, rather than the activation free energy, for the reductive dechlorination. Moreover, the intrinsic relationship of electrocatalysis and molecular electrochemistry is clearly indicated and quantitatively developed. These results may provide new insights in uncovering both the nature of catalytic property of Ag and the relationship of electrocatalysis and molecular electrochemistry for PCAs and other halocarbons.

  17. Synthesis of Cation and Water Free Cryptomelane Type OMS-2 Cathode Materials: The Impact of Tunnel Water on Electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Poyraz, Altug S.; Huang, Jianping; Zhang, Bingjie; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.

    2017-01-01

    Cryptomelane type manganese dioxides (α-MnO2, OMS-2) are interesting potential cathode materials due to the ability of their one dimensional (1D) tunnels to reversibly host various cations including Li+and an accessible stable 3+/4+ redox couple. Here, we synthesized metal cation free OMS-2 materials where the tunnels were occupied by only water and hydronium ions. Water was subsequently removed from the tunnels. Cation free OMS-2 and Dry-OMS-2 were used as cathodes in Li based batteries to investigate the role of tunnel water on their electrochemistry. The initial discharge capacity was higher for Dry-OMS-2 (252 mAh/g) compared to OMS-2 (194 mAh/g), however, after 100 cycles Dry-OMS-2 and OMS-2 delivered 137 mAh/g and 134 mAh/g, respectively. Li+ion diffusion was more facile for Dry-OMS as evidenced by rate capability, at 400 mA/g. Dry-OMS-2 delivered 135mAh/g whereas OMS-2 delivered ~115 mAh/g. This first report of the impact of tunnel water on the electrochemistry of OMS-2 type materials demonstrates that the presence of tunnel water in OMS-2 type materials negatively impacts the electrochemistry.

  18. The mechanism of the nano-CeO2 films deposition by electrochemistry method as coated conductor buffer layers

    International Nuclear Information System (INIS)

    Lu, Yuming; Cai, Shuang; Liang, Ying; Bai, Chuanyi; Liu, Zhiyong; Guo, Yanqun; Cai, Chuanbing

    2015-01-01

    Highlights: • Crack-free CeO 2 film thicker than 200 nm was prepared on NiW substrate by ED method. • Different electrochemical processes as hydroxide/metal mechanisms were identified. • The CeO 2 precursor films deposited by ED method were in nano-scales. - Abstract: Comparing with conventional physical vapor deposition methods, electrochemistry deposition technique shows a crack suppression effect by which the thickness of CeO 2 films on Ni–5 at.%W substrate can reach a high value up to 200 nm without any cracks, make it a potential single buffer layer for coated conductor. In the present work, the processes of CeO 2 film deposited by electrochemistry method are detailed investigated. A hydroxide reactive mechanism and an oxide reactive mechanism are distinguished for dimethyl sulfoxide and aqueous solution, respectively. Before heat treatment to achieve the required bi-axial texture performance of buffer layers, the precursor CeO 2 films are identified in nanometer scales. The crack suppression for electrochemistry deposited CeO 2 films is believed to be attributed to the nano-effects of the precursors

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

    Science.gov (United States)

    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

  20. 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

    Science.gov (United States)

    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

  1. Carbonyl Functionalized Single-Walled Carbon Nanotube-Hb Crosslinked Network: A Novel Platform for Studying Bio-Electrochemistry and Electrocatalysis of Hemoglobin.

    Science.gov (United States)

    Kafi, A K M; Yam, C C L; Azmi, N S; Yusoff, Mashitah M

    2018-04-01

    In this work, the direct electrochemistry of hemoglobin (Hb), which was immobilized on carbonyl functionalized single walled carbon nanotube (SWCNT) and deposited onto a gold (Au) electrode has been described. The synthesis of the network of crosslinked SWCNT/Hb was done with the help of crosslinking agent EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide). The UV-Vis and FTIR spectroscopy of SWCNT/Hb networks showed that Hb maintained its natural structure and kept good stability. In addition with this, scanning electron microscopy (SEM) illustrated that SWCNT/Hb networks had a featured layered structure and Hb being strongly liked with SWCNT surface. Cyclic voltammetry (CV) was used to study and to optimize the performance of the resulting modified electrode. The cyclic voltammetric (CV) responses of SWCNT/Hb networks in pH 7.0 exhibit prominent redox couple for the FeIII/II redox process with a midpoint potential of -0.46 V and -0.34, cathodic and anodic respectively. Furthermore, SWCNT/Hb networks are utilized for the detection of hydrogen peroxide (H2O2). Electrochemical measurements reveal that the resulting SWCNT/Hb electrodes display high electrocatalytic activity to H2O2 with high sensitivity, wide linear range, and low detection limit. Overall, the electrochemical results are due to excellent biocompatibility and excellent electron transport efficiency of CNT as well as high Hb loading and synergistic catalytic effect of the modified electrode toward H2O2.

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

    Science.gov (United States)

    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

  3. A detailed approach to model transport, heterogeneous chemistry, and electrochemistry in solid-oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Janardhanan, V.

    2007-07-01

    This dissertation layes out detailed descriptions for heterogeneous chemistry, electrochemistry, and porous media transport models to simulate solid oxide fuel cells (SOFCs). An elementary like heterogeneous reaction mechanism for the steam reforming of CH4 developed in our research group is used throughout this work. Based on assumption of hydrogen oxidation as the only electrochemical reaction and single step electron transfer reaction as rate limiting, a modified Butler-Volmer equation is used to model the electrochemistry. The pertinence of various porous media transport models such as Modified Fick Model (MFM), Dusty Gas Model (DGM), Mean Transport Pore Model, Modified Maxwell Stefan Model, and Generalized Maxwell Stefan Model under reaction conditions are studied. In general MFM and DGM predictions are in good agreement with experimental data. Physically realistic electrochemical model parameters are very important for fuel cell modeling. Button cell simulations are carried out to deduce the electrochemical model parameters, and those parameters are further used in the modeling of planar cells. Button cell simulations are carried out using the commercial CFD code FLUENT coupled with DETCHEM. For all temperature ranges the model works well in predicting the experimental observations in the high current density region. However, the model predicts much higher open circuit potentials than that observed in the experiments, mainly due to the absence of coking model in the elementary heterogeneous mechanism leading to nonequilibrium compositions. Furthermore, the study presented here employs Nernst equation for the calculation of reversible potential which is strictly valid only for electrochemical equilibrium. It is assumed that the electrochemical charge transfer reaction involving H2 is fast enough to be in equilibrium. However, the comparison of model prediction with thermodynamic equilibrium reveals that this assumption is violated under very low current

  4. Cognitive decline is associated with systemic oxidative stress: the EVA study. Etude du Vieillissement Artériel.

    Science.gov (United States)

    Berr, C; Balansard, B; Arnaud, J; Roussel, A M; Alpérovitch, A

    2000-10-01

    To determine whether systemic oxidative stress status is associated with cognitive decline. A longitudinal population-based study. A cohort study of older subjects in Nantes, France. A total of 1166 high cognitive functioning subjects aged 60 to 70 in the Etude du Vieillissement Arteriel (EVA) cohort with a 4 year follow-up. Subjects completed a baseline interview and a global cognitive test (Mini-Mental Status Examination (MMSE)). Blood samples were obtained at baseline to determine plasma levels of selenium, carotenoids, thiobarbituric acid reactant substances (TBARS), an indicator of lipoperoxidation, and red blood cell vitamin E. Risk of cognitive decline, defined as a loss of 3 points in MMSE score between baseline and the 4 year follow-up, was assessed by oxidative stress level. Subjects with the highest levels of TBARS show an increased risk of cognitive decline (adjusted odds ratio (OR) = 2.25; confidence interval (CI) 95% = 1.26-4.02). This result is reinforced in the lower antioxidant status subgroup. Subjects with low levels of selenium have an increased risk of cognitive decline (OR = 1.58; CI 95% = 1.08-2.31) after adjustment for various confounding factors. These results suggest that increased levels of oxidative stress and/or antioxidant deficiencies may pose risk factors for cognitive decline. The direct implication of oxidative stress in vascular and neurodegenerative mechanisms that lead to cognitive impairment should be further explored.

  5. Development of an analogue multiplexed regulation for periodic 1. order delayed processes; Etude et realisation d'une regulation analogique multiplexee pour processus aperiodiques du 1. ordre avec retard pur

    Energy Technology Data Exchange (ETDEWEB)

    Amblard, J C [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1967-07-15

    The present note deals with the study regulations of the sampled type, for 1. order process with simple delay. In order to obtain a good stability in such regulations, together with acceptable performances, it is interesting to use polynomial type correctors acting directly on the sampled error signals. The active elements of these correctors can be shared by all the channels to be controlled. Furthermore, the determination of the correction parameters results from an optimal study of the system. In the second part is described the construction of a multiplexed regulation for diffusion ovens. (author) [French] La presente note concerne l'etude des regulations de type echantillonne, pour processus du 1. ordre avec retard pur. Pour obtenir une bonne stabilite de telles regulations, ainsi que des performances correcte il est interessant d'utiliser des correcteurs de type polynomial, agissant directement sur les signaux d'erreur echantillonnes. Les elements actifs de ces correcteurs peuvent etre pris communs a toutes les voies a controler. D'autre part, la determination des parametres de correction decoula d'une etude optimale du systeme. Dans une seconde partie on decrit la realisation d'une regulation multiplexee de fours a diffusion. (auteur)

  6. Development of an analogue multiplexed regulation for periodic 1. order delayed processes; Etude et realisation d'une regulation analogique multiplexee pour processus aperiodiques du 1. ordre avec retard pur

    Energy Technology Data Exchange (ETDEWEB)

    Amblard, J.C. [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1967-07-15

    The present note deals with the study regulations of the sampled type, for 1. order process with simple delay. In order to obtain a good stability in such regulations, together with acceptable performances, it is interesting to use polynomial type correctors acting directly on the sampled error signals. The active elements of these correctors can be shared by all the channels to be controlled. Furthermore, the determination of the correction parameters results from an optimal study of the system. In the second part is described the construction of a multiplexed regulation for diffusion ovens. (author) [French] La presente note concerne l'etude des regulations de type echantillonne, pour processus du 1. ordre avec retard pur. Pour obtenir une bonne stabilite de telles regulations, ainsi que des performances correcte il est interessant d'utiliser des correcteurs de type polynomial, agissant directement sur les signaux d'erreur echantillonnes. Les elements actifs de ces correcteurs peuvent etre pris communs a toutes les voies a controler. D'autre part, la determination des parametres de correction decoula d'une etude optimale du systeme. Dans une seconde partie on decrit la realisation d'une regulation multiplexee de fours a diffusion. (auteur)

  7. Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions.

    Science.gov (United States)

    Samu, Gergely F; Scheidt, Rebecca A; Kamat, Prashant V; Janáky, Csaba

    2018-02-13

    The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and for assembling them into hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr 3 and hybrid organic-inorganic MAPbI 3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. The presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that comparisons can more easily be made.

  8. Pore-scale investigation of mass transport and electrochemistry in a solid oxide fuel cell anode

    Energy Technology Data Exchange (ETDEWEB)

    Grew, Kyle N.; Joshi, Abhijit S.; Peracchio, Aldo A.; Chiu, Wilson K.S. [Department of Mechanical Engineering, University of Connecticut, 191 Auditorium Road, Storrs, CT 06269-3139 (United States)

    2010-04-15

    The development and validation of a model for the study of pore-scale transport phenomena and electrochemistry in a Solid Oxide Fuel Cell (SOFC) anode are presented in this work. This model couples mass transport processes with a detailed reaction mechanism, which is used to model the electrochemical oxidation kinetics. Detailed electrochemical oxidation reaction kinetics, which is known to occur in the vicinity of the three-phase boundary (TPB) interfaces, is discretely considered in this work. The TPB regions connect percolating regions of electronic and ionic conducting phases of the anode, nickel (Ni) and yttria-stabilized zirconia (YSZ), respectively; with porous regions supporting mass transport of the fuel and product. A two-dimensional (2D), multi-species lattice Boltzmann method (LBM) is used to describe the diffusion process in complex pore structures that are representative of the SOFC anode. This diffusion model is discretely coupled to a kinetic electrochemical oxidation mechanism using localized flux boundary conditions. The details of the oxidation kinetics are prescribed as a function of applied activation overpotential and the localized hydrogen and water mole fractions. This development effort is aimed at understanding the effects of the anode microstructure within TPB regions. This work describes the methods used so that future studies can consider the details of SOFC anode microstructure. (author)

  9. Colloid electrochemistry of conducting polymer: towards potential-induced in-situ drug release

    International Nuclear Information System (INIS)

    Sankoh, Supannee; Vagin, Mikhail Yu.; Sekretaryova, Alina N.; Thavarungkul, Panote; Kanatharana, Proespichaya; Mak, Wing Cheung

    2017-01-01

    Highlights: • Pulsed electrode potential induced an in-situ drug release from dispersion of conducting polymer microcapsules. • Fast detection of the released drug within the colloid microenvironment. • Improved the efficiency of localized drug release at the electrode interface. - Abstract: Over the past decades, controlled drug delivery system remains as one of the most important area in medicine for various diseases. We have developed a new electrochemically controlled drug release system by combining colloid electrochemistry and electro-responsive microcapsules. The pulsed electrode potential modulation led to the appearance of two processes available for the time-resolved registration in colloid microenvironment: change of the electronic charge of microparticles (from 0.5 ms to 0.1 s) followed by the drug release associated with ionic equilibration (1–10 s). The dynamic electrochemical measurements allow the distinction of drug release associated with ionic relaxation and the change of electronic charge of conducting polymer colloid microparticles. The amount of released drug (methylene blue) could be controlled by modulating the applied potential. Our study demonstrated a surface-potential driven controlled drug release of dispersion of conducting polymer carrier at the electrode interfaces, while the bulk colloids dispersion away from the electrode remains as a reservoir to improve the efficiency of localized drug release. The developed new methodology creates a model platform for the investigations of surface potential-induced in-situ electrochemical drug release mechanism.

  10. Simulating Electrochemistry of Hydrothermal Vents on Enceladus and Other Ocean Worlds

    Science.gov (United States)

    Barge, L. M.; Krause, F. C.; Jones, J. P.; Billings, K.; Sobron, P.

    2017-12-01

    Gradients generated in hydrothermal systems provide a significant source of free energy for chemosynthetic life, and may play a role in present-day habitability on ocean worlds such as Enceladus that are thought to host hydrothermal activity. Hydrothermal vents are similar in some ways to typical fuel cell devices: redox/pH gradients between seawater and hydrothermal fluid are analogous to the oxidant and fuel reservoirs; conductive natural mineral deposits are analogous to electrodes; and, in hydrothermal chimneys, the porous chimney wall can function as a separator or ion-exchange membrane. Electrochemistry, founded on quantitative study of redox and other chemical disequilibria as well as the chemistry of interfaces, is uniquely suited to studying these systems. We have performed electrochemical studies to better understand the catalytic potential of seafloor minerals and vent chimneys, using samples from a black smoker vent chimney as an initial demonstration. Fuel cell experiments with electrodes made from black smoker chimney material accurately simulated the redox reactions that occur in a geological setting with this particular catalyst. Similar methods with other geo-catalysts (natural or synthetic) could be utilized to test which redox reactions or metabolisms could be driven in other hydrothermal systems, including putative vent systems on other worlds.

  11. Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions

    KAUST Repository

    Samu, Gergely F.; Scheidt, Rebecca A; Kamat, Prashant V.; Janá ky, Csaba

    2017-01-01

    The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and to assemble their hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr3 and hybrid organic-inorganic MaPbI3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. We believe that the presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that easier comparisons can be made.

  12. Liquid / liquid biphasic electrochemistry in ultra-turrax dispersed acetonitrile / aqueous electrolyte systems

    International Nuclear Information System (INIS)

    Watkins, John D.; Amemiya, Fumihiro; Atobe, Mahito; Bulman-Page, Philip C.; Marken, Frank

    2010-01-01

    Unstable acetonitrile | aqueous emulsions generated in situ with ultra-turrax agitation are investigated for applications in dual-phase electrochemistry. Three modes of operation for liquid / liquid aqueous-organic electrochemical processes are demonstrated with no intentionally added electrolyte in the organic phase based on (i) the formation of a water-soluble product in the aqueous phase in the presence of the organic phase, (ii) the formation of a product and ion transfer at the liquid / liquid-electrode triple phase boundary, and (iii) the formation of a water-insoluble product in the aqueous phase which then transfers into the organic phase. A three-electrode electrolysis cell with ultra-turrax agitator is employed and characterised for acetonitrile / aqueous 2 M NaCl two phase electrolyte. Three redox systems are employed in order to quantify the electrolysis cell performance. The one-electron reduction of Ru(NH 3 ) 6 3+ in the aqueous phase is employed to determine the rate of mass transport towards the electrode surface and the effect of the presence of the acetonitrile phase. The one-electron oxidation of n-butylferrocene in acetonitrile is employed to study triple phase boundary processes. Finally, the one-electron reduction of cobalticenium cations in the aqueous phase is employed to demonstrate the product transfer from the electrode surface into the organic phase. Potential applications in biphasic electrosynthesis are discussed.

  13. Synthesis and electrochemistry of tri- and tetranuclear polypyridine derivations of ruthenium

    International Nuclear Information System (INIS)

    Francis, A.M.A.

    1990-01-01

    The synthesis of clusters of ruthenium is the focus of this work. The electrochemistry of metal cluster derivatives of ruthenium, iron and osmium are reviewed. The ability of these compounds to undergo more than one electron transfer reaction and to act as electron reservoirs is evident. The synthesis and characterisation of a range of polypyridine derivatives of [Ru 3 (CO) 12 ]; [Ru 3 (CO) 10 (napy)]; [Ru 3 (CO) 10 (bipy)]; [Ru 4 H 4 (CO) 12 ]; [Ru 4 H 4 (CO) 8 (bipy) 2 ] and [Ru 4 H 4 (CO) 10 (bipy)] were dealt with. The crystal structures of [Ru 3 (CO) 10 (napy)] and [Ru 4 H 4 (CO) 10 (bipy)] were also determined. The six compounds were fully investigated and a mechanism for their electrochemical reduction was postulated based on their observed experimental data, and that of the relevant compounds. The techniques used are also described and a brief introduction to the actual theory and practise of these techniques is discussed. 132 refs., 33 figs., 22 tabs

  14. Corrosion of structural materials and electrochemistry in high temperature water of nuclear power systems

    International Nuclear Information System (INIS)

    Uchida, Shunsuke

    2008-01-01

    The latest experiences with corrosion in the cooling systems of nuclear power plants are reviewed. High temperature cooling water causes corrosion of structural materials, which often leads to adverse effects in the plants, e.g., increased shutdown radiation, generation of defects in materials of major components and fuel claddings, and increased volume of radwaste sources. Corrosion behavior is greatly affected by water quality and differs according to the water quality values and the materials themselves. In order to establish reliable operation, each plant requires its own unique optimal water chemistry control based on careful consideration of its system, materials and operational history. Electrochemistry is one of the key issues that determine corrosion-related problems, but it is not the only issue. Most corrosion-related phenomena, e.g., flow accelerated corrosion (FAC), intergranular stress corrosion cracking (IGSCC), primary water stress corrosion cracking (PWSCC) and thinning of fuel cladding materials, can be understood based on an electrochemical index, e.g., the electrochemical corrosion potential (ECP), conductivities and pH. The most important electrochemical index, the ECP, can be measured at elevated temperature and applied to in situ sensors of corrosion conditions to detect anomalous conditions of structural materials at their very early stages. (orig.)

  15. Actinide, lanthanide and fission product speciation and electrochemistry in high and low temperature ionic melts

    Energy Technology Data Exchange (ETDEWEB)

    Bhatt, Anand I.; Kinoshita, Hajime; Koster, Anne L.; May, Iain; Sharrad, Clint A.; Volkovich, Vladimir A.; Fox, O. Danny; Jones, Chris J.; Lewin, Bob G.; Charnock, John M.; Hennig, Christoph

    2004-07-01

    There is currently a great deal of research interest in the development of molten salt technology, both classical high temperature melts and low temperature ionic liquids, for the electrochemical separation of the actinides from spent nuclear fuel. We are interested in gaining a better understanding of actinide and key fission product speciation and electrochemical properties in a range of melts. Our studies in high temperature alkali metal melts (including LiCl and LiCl-KCl and CsCl-NaCl eutectics) have focussed on in-situ species of U, Th, Tc and Ru using X-ray absorption spectroscopy (XAS, both EXAFS and XANES) and electronic absorption spectroscopy (EAS). We report unusual actinide speciation in high temperature melts and an evaluation of the likelihood of Ru or Tc volatilization during plant operation. Our studies in lower temperature melts (ionic liquids) have focussed on salts containing tertiary alkyl group 15 cations and the bis(tri-fluor-methyl)sulfonyl)imide anion, melts which we have shown to have exceptionally wide electrochemical windows. We report Ln, Th, U and Np speciation (XAS, EAS and vibrational spectroscopy) and electrochemistry in these melts and relate the solution studies to crystallographic characterised benchmark species. (authors)

  16. Actinide, lanthanide and fission product speciation and electrochemistry in high and low temperature ionic melts

    International Nuclear Information System (INIS)

    Bhatt, Anand I.; Kinoshita, Hajime; Koster, Anne L.; May, Iain; Sharrad, Clint A.; Volkovich, Vladimir A.; Fox, O. Danny; Jones, Chris J.; Lewin, Bob G.; Charnock, John M.; Hennig, Christoph

    2004-01-01

    There is currently a great deal of research interest in the development of molten salt technology, both classical high temperature melts and low temperature ionic liquids, for the electrochemical separation of the actinides from spent nuclear fuel. We are interested in gaining a better understanding of actinide and key fission product speciation and electrochemical properties in a range of melts. Our studies in high temperature alkali metal melts (including LiCl and LiCl-KCl and CsCl-NaCl eutectics) have focussed on in-situ species of U, Th, Tc and Ru using X-ray absorption spectroscopy (XAS, both EXAFS and XANES) and electronic absorption spectroscopy (EAS). We report unusual actinide speciation in high temperature melts and an evaluation of the likelihood of Ru or Tc volatilization during plant operation. Our studies in lower temperature melts (ionic liquids) have focussed on salts containing tertiary alkyl group 15 cations and the bis(tri-fluor-methyl)sulfonyl)imide anion, melts which we have shown to have exceptionally wide electrochemical windows. We report Ln, Th, U and Np speciation (XAS, EAS and vibrational spectroscopy) and electrochemistry in these melts and relate the solution studies to crystallographic characterised benchmark species. (authors)

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

    Science.gov (United States)

    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.

  18. Electrochemistry, polymers and opto-electronic devices: a combination with a future

    Directory of Open Access Journals (Sweden)

    De Paoli Marco-A.

    2002-01-01

    Full Text Available Electrochemistry came into life with the invention of the pile, by Volta in 1800. He combined different metal discs with a piece of tissue, swollen with an aqueous salt solution. The so-called Pila di Volta used a polymer for the first time in an electrochemical device and can be seen as a powerful idea to create new devices. Recently, polymers became an alternative to make thin and flexible devices. Thus, we find transparent plastic electrodes based on poly(ethylene terephtalate coated with a transition metal oxide. There are also polymer electrolytes based on complexes of inorganic salts and poly(ethylene oxide derivatives, with reasonable ionic conductivity in the absence of solvents. Finally, the electroactive polymers are efficient substitutes for the inorganic semiconductors because they can be synthetically tailored to produce the desired electronic answer. Combining these materials it is possible to assemble different types of electro-optical devices, like electrochromic, photoelectrochemical and light-emitting electrochemical cells.

  19. Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions

    KAUST Repository

    Samu, Gergely F.

    2017-12-06

    The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and to assemble their hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr3 and hybrid organic-inorganic MaPbI3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. We believe that the presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that easier comparisons can be made.

  20. Electrochemistry of immobilized particles and droplets experiments with three-phase electrodes

    CERN Document Server

    Scholz, Fritz; Gulaboski, Rubin; Schröder, Uwe

    2014-01-01

    This second edition of a successful and highly-accessed monograph has been extended by more than 100 pages. It includes an enlarged coverage of applications for materials characterization and analysis. Also a more detailed description of strategies for determining free energies of ion transfer between miscible liquids is provided. This is now possible with a "third-phase strategy" which the authors explain from theoretical and practical points of view. The book is still the only one detailing strategies for solid state electroanalysis. It also features the specific potential of the techniques to use immobilized particles (for studies of solid materials) and of immobilized droplets of immiscible liquids for the purpose of studying the three-phase electrochemistry of these liquids. This also includes studies of ion transfer between aqueous and immiscible non-aqueous liquids. The bibliography of all published papers in this field of research has been expanded from 318 to now 444 references in this second editi...

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

    Science.gov (United States)

    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.

  2. Forensic electrochemistry: indirect electrochemical sensing of the components of the new psychoactive substance "Synthacaine".

    Science.gov (United States)

    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".

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  5. Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions

    Science.gov (United States)

    2017-01-01

    The unique optoelectronic properties of lead halide perovskites have triggered a new wave of excitement in materials chemistry during the past five years. Electrochemistry, spectroelectrochemistry, and photoelectrochemistry could be viable tools both for analyzing the optoelectronic features of these materials and for assembling them into hybrid architectures (e.g., solar cells). At the same time, the instability of these materials limits the pool of solvents and electrolytes that can be employed in such experiments. The focus of our study is to establish a stability window for electrochemical tests for all-inorganic CsPbBr3 and hybrid organic–inorganic MAPbI3 perovskites. In addition, we aimed to understand the reduction and oxidation events that occur and to assess the damage done during these processes at extreme electrochemical conditions. In this vein, we demonstrated the chemical, structural, and morphological changes of the films in both reductive and oxidative environments. Taking all these results together as a whole, we propose a set of boundary conditions and protocols for how electrochemical experiments with lead halide perovskites should be carried out and interpreted. The presented results will contribute to the understanding of the electrochemical response of these materials and lead to a standardization of results in the literature so that comparisons can more easily be made. PMID:29503507

  6. Magnetic resonance studies of solid polymers; Etude des polymeres solides par resonance magnetique

    Energy Technology Data Exchange (ETDEWEB)

    Lenk, R [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    This paper is a review of the application of nuclear magnetic resonance (NMR) to solid polymers. In the first, theoretical part, the elements of the theory of NMR, which are necessary for the study of the properties of solid polymers are discussed: the moments method, nuclear relaxation and the distribution of correlation times. In the second part the experimental results are presented. (author) [French] Cette etude est une recherche bibliographique sur l'application de la resonance magnetique nucleaire (RMN) aux polymeres solides. Dans la premiere partie theorique on discute les elements de la theorie de RMN, necessaires pour l'etude des proprietes des polymeres solides: la methode des moments, la relaxation nucleaire et la distribution des temps de correlation. La deuxieme partie presente les resultats des experiences. (auteur)

  7. Iron(III) diethylenetriaminepentaacetic acid complex on polyallylamine functionalized multiwalled carbon nanotubes: immobilization, direct electrochemistry and electrocatalysis.

    Science.gov (United States)

    Liu, Hailing; Cui, Yanyun; Li, Pan; Zhou, Yiming; Zhu, Xiaoshu; Tang, Yawen; Chen, Yu; Lu, Tianhong

    2013-05-07

    A nonenzymatic iron(III) diethylenetriaminepentaacetic acid (Fe(III)-DETPA) complex based amperometric sensor for the analytical determination of hydrogen peroxide was developed. By combining the electrostatic interaction between the Fe(III)-DETPA complex and polyallylamine (PAH) functionalized multiwalled carbon nanotubes (MWCNTs) as well as the ionotropic crosslinking interaction between PAH and ethylenediamine-tetramethylene phosphonic acid (EDTMP), the electroactive Fe(III)-DETPA complex was successfully incorporated within the MWCNT matrix, and firmly immobilized on the Au substrate electrode. The fabricated electrochemical sensor was characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical methods. The influences of solution pH and ionic strength on the electrochemical sensor were investigated. The prepared electrochemical sensor had a fast response to hydrogen peroxide (<3 s) and an excellent linear range of concentration from 1.25 × 10(-8) to 4.75 × 10(-3) M with a detection limit of 6.3 × 10(-9) M under the optimum conditions.

  8. A highly efficient nano-cluster artificial peroxidase and its direct electrochemistry on a nano complex modified glassy carbon electrode.

    Science.gov (United States)

    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.

  9. The Investigation of Electrochemistry Behaviors of Tyrosinase Based on Directly-Electrodeposited Grapheneon Choline-Gold Nanoparticles.

    Science.gov (United States)

    He, Yaping; Yang, Xiaohui; Han, Quan; Zheng, Jianbin

    2017-06-23

    A novel catechol (CA) biosensor was developed by embedding tyrosinase (Tyr) onto in situ electrochemical reduction graphene (EGR) on choline-functionalized gold nanoparticle (AuNPs-Ch) film. The results of UV-Vis spectra indicated that Tyr retained its original structure in the film, and an electrochemical investigation of the biosensor showed a pair of well-defined, quasi-reversible redox peaks with E pa = -0.0744 V and E pc = -0.114 V (vs. SCE) in 0.1 M, pH 7.0 sodium phosphate-buffered saline at a scan rate of 100 mV/s. The transfer rate constant k s is 0.66 s -1 . The Tyr-EGR/AuNPs-Ch showed a good electrochemical catalytic response for the reduction of CA, with the linear range from 0.2 to 270 μM and a detection limit of 0.1 μM (S/N = 3). The apparent Michaelis-Menten constant was estimated to be 109 μM.

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

    Science.gov (United States)

    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.

  11. Anthraquinone as a redox label for DNA. Synthesis, enzymatic incorporation and electrochemistry of anthraquinone modified nucleosides, nucleotides and DNA

    Czech Academy of Sciences Publication Activity Database

    Balintová, J.; Havran, Luděk; Fojta, Miroslav; Hocek, Michal

    2012-01-01

    Roč. 106, - (2012), s1033-s1033 ISSN 0009-2770. [EuCheMS Chemistry Congress /4./. 26.08.2012-30.08.2012, Prague] R&D Projects: GA ČR GA203/09/0317; GA MŠk LC512; GA MŠk 1M0508; GA AV ČR(CZ) IAA400040901 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z50040702 Keywords : nucleosides * oligonucleotides * electrochemistry Subject RIV: CC - Organic Chemistry

  12. Composition-Graded MoWSx Hybrids with Tailored Catalytic Activity by Bipolar Electrochemistry.

    Science.gov (United States)

    Tan, Shu Min; Pumera, Martin

    2017-12-06

    Among transition metal dichalcogenide (TMD)-based composites, TMD/graphene-related material and bichalcogen TMD composites have been widely studied for application toward energy production via the hydrogen evolution reaction (HER). However, scarcely any literature explored the possibility of bimetallic TMD hybrids as HER electrocatalysts. The use of harmful chemicals and harsh preparation conditions in conventional syntheses also detracts from the objective of sustainable energy production. Herein, we present the conservational alternative synthesis of MoWS x via one-step bipolar electrochemical deposition. Through bipolar electrochemistry, the simultaneous fabrication of composition-graded MoWS x hybrids, i.e., sulfur-deficient Mo x W (1-x) S 2 and Mo x W (1-x) S 3 (MoWS x /BPE cathodic and MoWS x /BPE anodic , respectively) under cathodic and anodic overpotentials, was achieved. The best-performing MoWS x /BPE cathodic and MoWS x /BPE anodic materials exhibited Tafel slopes of 45.7 and 50.5 mV dec -1 , together with corresponding HER overpotentials of 315 and 278 mV at -10 mA cm -2 . The remarkable HER activities of the composite materials were attributed to their small particle sizes, as well as the near-unity value of their surface Mo/W ratios, which resulted in increased exposed HER-active sites and differing active sites for the concurrent adsorption of protons and desorption of hydrogen gas. The excellent electrocatalytic performances achieved via the novel methodology adopted here encourage the empowerment of electrochemical deposition as the foremost fabrication approach toward functional electrocatalysts for sustainable energy generation.

  13. Electrochemistry of oxo-technetium(V) complexes containing Schiff base and 8-quinolinol ligands

    International Nuclear Information System (INIS)

    Refosco, F.; Mazzi, U.; Deutsch, E.; Kirchhoff, J.R.; Heineman, W.R.; Seeber, R.

    1988-01-01

    The electrochemistry of six-coordinate, monooxo technetium(V) complexes containing Schiff base ligands has been studied in acetonitrile and N,N'-dimethylformamide solutions. The complexes have the general formula TcOCl(L B ) 2 or TcO(L T )(L B ), where L B represents a bidentate-N,O Schiff base ligand or a bidentate-N,O 8-quinolinol ligand and L T represents a tridentate-O,N,O Schiff base ligand. Cyclic voltammetry at a platinum-disk electrode, controlled-potential coulometry, and thin-layer spectroelectrochemistry were used to probe both the oxidation and the reduction of these complexes. The results of these studies, and previously reported results on the analogous Re(V) complexes, can be understood within a single general reaction scheme. The salient features of this scheme are (i) one-electron reduction of Tc(V) to Tc(IV), (ii) subsequent loss of a ligand situated cis to the Tc≡O linkage, and (iii) subsequent isomerization of this unstable Tc(IV) product to more stable complex in which the site trans to the Tc≡O linkage is vacant. The Tc(IV) complexes can also be reduced to analogous Tc(III) species, which appear to undergo the same ligand loss and isomerization reactions. The technetium complexes are 400-500 mV easier to reduce than are their rhenium analogues. The 8-quinolinol ligands, and especially the 5-nitro derivative, both thermodynamically and kinetically stabilize the Tc(IV) and Tc(III) oxidation states. These electrogenerated species are unusual in that they constitute the bulk of the known examples of monomeric Tc(IV) and Tc(III) complexes containing only N- and O-donating ligands. 34 refs., 9 figs., 1 tab

  14. Endogenous minerals have influences on surface electrochemistry and ion exchange properties of biochar.

    Science.gov (United States)

    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. The electrochemistry of chromium, chromium-boron and chromium-phosphorus alloys

    International Nuclear Information System (INIS)

    Moffat, T.P.; Ruf, R.R.; Latanision, R.M.

    1987-01-01

    It is fairly well established that chromium-metalloid interactions represent the key to understanding the remarkable corrosion behavior of TM-Cr-M glasses; (Fe, Ni, Co,...)-Cr-(P, Si, C, S). The character and kinetics of passive film growth on the glasses are being studied ni order to assess the role of the film former, chromium, and the metalloids in the passivation process. A series of thin film microcrystalline chromium, Cr-B and Cr-P binary alloys have been fabricated by physical vapor deposition techniques. Vacuum melted conventionally processed chromium has also been studied. Examination of these materials in lM H/sub 2/SO/sub 4/ and lM HCl by voltammetry, potentiostatic and impedance techniques yields the following conclusion: 1. Pure chromium with a grain size varying from < 400 A to 0.5 mm exhibits no well defined differences in electrochemical behavior in lM H/sub 2/SO/sub 4/. 2. The tremendous corrosion resistance of Cr-B alloys has been confirmed. 3. The beneficial effects observed for boron alloyed with chromium may be considered surprising in view of the neutral/negative influence of alloying boron with iron, i.e. Fe/sub 80/B/sub 20/. 4. The interaction of the electrochemistry of the metalloid constituent with that of the transition base element determines the corrosion behavior. 5. Preliminary work with Cr-P alloys indicates that certain compositions exhibit promising properties - certain films were found to be intact after two days of immersion in concentrated HCl. Further work is in progress

  16. Synthesis, electrochemistry, and electrogenerated chemiluminescence of two BODIPY-appended bipyridine homologues.

    Science.gov (United States)

    Qi, Honglan; Teesdale, Justin J; Pupillo, Rachel C; Rosenthal, Joel; Bard, Allen J

    2013-09-11

    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 it suggests that a new emissive species is formed from the bpy-BODIPY luminophores during the annihilation process.

  17. Electrochemically modulated liquid chromatography: Theoretical investigations and applications from the perspectives of chromatography and interfacial electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Keller, David W. [Iowa State Univ., Ames, IA (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  19. Integration of electrochemistry with ultra-performance liquid chromatography/mass spectrometry.

    Science.gov (United States)

    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.

  20. Synthesis, Electrochemistry and Electrogenerated Chemiluminesce of two BODIPY-Appended Bipyridine Homologues

    Science.gov (United States)

    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

  1. The significant role of carboxylated carbonaceous fragments in the electrochemistry of carbon nanotubes.

    Science.gov (United States)

    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.

  2. Integration of Electrochemistry with Ultra Performance Liquid Chromatography/Mass Spectrometry (UPLC/MS)

    Science.gov (United States)

    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

  3. Probing into the effects of a magnetic field on the electrode processes of iron in sulphuric acid solutions with dichromate based on the fundamental electrochemistry kinetics

    International Nuclear Information System (INIS)

    Lu Zhanpeng; Huang Delun; Yang Wu

    2005-01-01

    The effects of an applied magnetic field on the electrode processes of iron in sulphuric acid solutions with dichromate have been investigated by electrochemical measurements. Open circuit potentials, cathodic and anodic polarisation curves, values of polarisation resistance were measured in the presence or absence of a 0.4 T horizontal magnetic field (HMF). A potentiostatic polarisation plus magnetic field perturbation technique was used to study the effect of the magnetic field on open circuit corrosion. Cathodic reaction rates at open circuit potentials for iron in sulphuric acid solutions containing dichromate ions are controlled by both the electron-transfer process and the diffusion process. A magnetic field made the open circuit potential move in the positive direction, and changes of the open circuit potentials due to the magnetic field increase with increasing dichromate concentration. When iron was potentiostatically polarised at open circuit potentials in the absence of a magnetic field, a cathodic current was observed after a magnetic field was imposed. Such cathodic currents induced by the magnetic field increases with increasing dichromate concentration. The positive shifts of open circuit potential, the decrease of polarisation resistance, and the occurrence of cathodic currents induced by the magnetic field are caused by the accelerating effect of magnetic field on the cathodic diffusion process. Measured current densities showed lower, equal, or higher values in the presence of the magnetic field than those in the absence of a magnetic field at certain anodic potentials. This effect of the magnetic field is related to the contribution of the cathodic and anodic reactions to the measured current and the types of rate-determining steps for each reaction at certain potentials. The applied magnetic field significantly decreased the polarisation resistance. The experimental results in this paper are formulated based on the fundamental electrochemistry

  4. Structure, electrochemistry and spectroscopy of a new diacylhydrazido-bridged diruthenium complex with a strongly near-infrared absorbing RuIIIRuII intermediate

    Czech Academy of Sciences Publication Activity Database

    Jana, R.; Sarkar, B.; Bubrin, D.; Fiedler, Jan; Kaim, W.

    2010-01-01

    Roč. 13, č. 10 (2010), s. 1160-1162 ISSN 1387-7003 R&D Projects: GA MŠk OC 140; GA MŠk OC09043 Institutional research plan: CEZ:AV0Z40400503 Keywords : crystal structure * hydrazido ligand * near-infrared ruthenium Subject RIV: CG - Electrochemistry Impact factor: 1.974, year: 2010

  5. Stereoisomeric products of electrochemical reduction of heterocyclic Fischer aminocarbene Cr(0) complexes. Development of the electrochemistry-mass spectrometry tandem approach using biphasic (acetonitrile-hexane) preparative electrolysis

    Czech Academy of Sciences Publication Activity Database

    Metelková, R.; Hoskovcová, I.; Polášek, Miroslav; Urban, Jiří; David, T.; Ludvík, Jiří

    2015-01-01

    Roč. 162, APR 2015 (2015), s. 17-23 ISSN 0013-4686 R&D Projects: GA ČR GAP206/11/0727 Institutional support: RVO:61388955 Keywords : Fischer aminocarbene complexes biphasic electrolysis * EC-MS * HPLC-NMR Subject RIV: CG - Electrochemistry Impact factor: 4.803, year: 2015

  6. High Performance Liquid Chromatography/Electrochemistry/High Resolution Electrospray Ionization-Mass Spectrometry (HPLC/EC/HR ESI-MS) Characterization of Selected Cytokinins Oxidation Products

    Czech Academy of Sciences Publication Activity Database

    Karady, Michal; Novák, Ondřej; Horna, A.; Strnad, Miroslav; Doležal, Karel

    2015-01-01

    Roč. 27, č. 2 (2015), s. 406-414 ISSN 1040-0397 R&D Projects: GA MŠk(CZ) LO1204 Institutional support: RVO:61389030 Keywords : Electrochemistry * Cytokinin * Oxidative metabolism Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.471, year: 2015

  7. Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

    Science.gov (United States)

    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

  8. Theoretical study of the paramagnetic scattering of neutrons; Etude theorique de la diffusion paramagnetique des neutrons

    Energy Technology Data Exchange (ETDEWEB)

    Saint-James, D [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1962-02-15

    diverses diffusions (elastique et inelastiques) est calculee pour les terres rares soumises a l'action d'un champ cristallin de symetrie cubique, pour les sesquioxydes d'holmium et d'erbium et pour le chlorure ferreux anhydre (Cl{sub 2}Fe). Elle est suffisamment forte pour permettre une detection experimentale, fournissant ainsi une determination directe de la distance des niveaux par mesure de la variation de longueur d'onde du neutron. Il est, de plus, remarquable que, dans le cas du neodyme, de l'holium et de l'erbium, la section efficace totale calculee pour des neutrons de longueur d'onde aux alentours de l'angstrom soit peu sensible aux effets du champ cristallin. On compare les resultats des calculs ci-dessus aux etudes experimentales existantes. On examine egalement l'influence du moment orbital sur la dependance angulaire de la diffusion pour des ions polarises. La loi I = I{sub 0}sin{sup 2}{beta} n'est qu'approchee; on en donne les limites de validite. On envisage enfin l'influence des interactions d'echange entre les ions magnetiques. Les raies de diffusion elastiques et inelastiques sont elargies. Le comportement de la largeur de raie, avec la longueur du vecteur de diffusion k, est different de celui obtenu dans le cas ou le niveau fondamental de l'ion magnetique est defini par un moment cinetique J . La largeur de raie ne tend pas vers zero avec K. (auteur)

  9. Etude de l'impact de la variation de la température sur les activités ...

    African Journals Online (AJOL)

    Etude de l'impact de la variation de la température sur les activités microbiennes : application à une population de Listeria monocytogenes CIP 7831, Listeria monocytogenes Scott A CIP 103575 et Escherichia coli ATCC 25922.

  10. Bio-metric study of pig karyotype; Etude biometrique du caryotype du porc

    Energy Technology Data Exchange (ETDEWEB)

    Haag, J; Lacourly, N; Nizza, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1969-07-01

    This study has a twofold purpose, the former is to determine the swine karyotype as accurately as possible, the latter is to try and develop a method of automatic classification and to show its possibilities and limits. (authors) [French] Cette etude a un double objet: d'une part, de definir de la facon aussi precise que possible le caryotype du porc et d'autre part, de tenter une methode de classification automatique et d'en montrer les possibilites ainsi que les limites. (auteurs)

  11. Inherent Electrochemistry and Charge Transfer Properties of Few-Layer Two Dimensional Ti3C2Tx MXene

    KAUST Repository

    Nayak, Pranati

    2018-05-25

    We report the effect of Ti3C2Tx MXene flake thickness on its inherent electrochemistry and heterogeneous charge transfer characteristics. It is shown that the Ti3C2Tx undergoes irreversible oxidation in the positive potential window, which strongly depends on the flake thickness and pH of the electrolyte. Few-layer Ti3C2Tx exhibits faster electron transfer kinetics (k0=0.09533 cm/s) with Fe(CN)64−/3− redox mediator compared to multi-layer Ti3C2Tx (k0= 0.00503 cm/s). In addition, few-layer free standing Ti3C2Tx film electrode remains intact after enduring irreversible oxidation.

  12. Synthesis and electrochemistry properties of Sn-Sb ultrafine particles as anode of lithium-ion batteries

    International Nuclear Information System (INIS)

    Wang, Zhong; Tian, Wenhuai; Li, Xingguo

    2007-01-01

    Ultrafine particles of Sn-Sb alloys with different chemical composition have been prepared by hydrogen plasma-metal reaction. Structure, morphology, size and chemical composition of the Sn-Sb ultrafine particles were investigated by transmission electron microscopy, X-ray diffraction, BET gas adsorption, and induction-coupled plasma spectroscopy. It was found that all the particles have spherical shapes, with average particle size in the range of 100-300 nm. The electrochemistry properties as an alternative anode material for lithium-ion batteries have been characterized by constant current cycling and cyclic voltammetry. Electrochemical measurements showed that the alloys with Sn-46.5 at.% Sb have best reversible capacity and capacity retention. It exhibited a high reversible lithium-ion storage capacity of 701 mAh g -1 in the initial cycle, which has remained at 81% (i.e., 566 mAh g -1 ) of its original capacity after 20 cycles

  13. Inherent Electrochemistry and Charge Transfer Properties of Few-Layer Two Dimensional Ti3C2Tx MXene

    KAUST Repository

    Nayak, Pranati; Jiang, Qiu; Mohanraman, Rajeshkumar; Anjum, Dalaver H.; Hedhili, Mohamed N.; Alshareef, Husam N.

    2018-01-01

    We report the effect of Ti3C2Tx MXene flake thickness on its inherent electrochemistry and heterogeneous charge transfer characteristics. It is shown that the Ti3C2Tx undergoes irreversible oxidation in the positive potential window, which strongly depends on the flake thickness and pH of the electrolyte. Few-layer Ti3C2Tx exhibits faster electron transfer kinetics (k0=0.09533 cm/s) with Fe(CN)64−/3− redox mediator compared to multi-layer Ti3C2Tx (k0= 0.00503 cm/s). In addition, few-layer free standing Ti3C2Tx film electrode remains intact after enduring irreversible oxidation.

  14. The formation of scientists and technicians at the 'Centre d'Etudes Nucleaires' at Saclay

    International Nuclear Information System (INIS)

    Debiesse, J.

    1958-01-01

    The considerable needs in research workers and scientists which are asked by the nuclear energy obliged the Commissariat a l'Energie atomique to deal with a particular effort to increase the quantitative and qualitative formation of scientists. Most various ways have been used. 1- A National Institute of Nuclear Sciences and Nuclear Techniques was created, by a joint decree of the Prime Minister and the Minister for National Education (june 18, 1957). This Institute of Higher Teaching (250 students) indulges in the following matters: atomic engineering, quantum mechanics, theory and technic of particle accelerators, special metallurgy, radiobiology, thermic and mechanics of fluids. 2- An associated centre of the 'Conservatoire National des Arts et Metiers' was created (200 students) for technical assistants, drawers, etc. 3- In contribution with both electronic industry and Ministry of Work, the Centre d'Etudes Nucleaires contributes to an accelerated formation of technical assistants into Professional Centres. Conclusion: Training of scientists and research workers is one of the most important activities of the Centre d'Etudes Nucleaires de Saclay. Without losing its technical efficiency, it has supplied and varied means adapted to the various purposes that we shall reach. (author) [fr

  15. Contribution to the study of {beta} disintegration and of nuclear structure using experiments on certain {beta}-{gamma} cascades: 198{sub Au}, 86{sub Rb}, 170{sub Tm}; Contribution a l'etude de la desintegration beta et a l'etude de la structure nucleaire a l'aide d'experiences sur certaines cascades beta-gamma: 198{sub Au}, 86{sub Rb}, 170{sub Tm}

    Energy Technology Data Exchange (ETDEWEB)

    Lachkar, J. [Commissariat a l' Energie Atomique, Bruyeres-le-Chatel (France). Centre d' Etudes; Paris-11 Univ., fabulte des Sciences 91 - Orsay (France)

    1969-07-01

    {beta}{gamma} directional angular correlations and shapes of inner beta spectra leading to the first excited level of the final nucleus enable one to determine the nuclear matrix elements typical of the {beta} transition. In the three observed first forbidden cases: {sup 170}Tm, {sup 86}Rb, {sup 198}Au, these matrix elements do not confirm the independent shell model theory. Other hypotheses are then suggested and discussed. (author) [French] Les experiences de correlation angulaire {beta}{gamma} et l'etude du spectre {beta} conduisant au premier niveau excite du noyau final permettent de determiner les elements de matrices nucleaires caracteristiques de cette transition. Dans les trois cas etudies (transitions une fois interdites): {sup 170}Tm, {sup 86}Rb, {sup 198}Au, ces elements de matrices ne peuvent etre retrouves a l'aide du modele en couches et a particules independantes. D'autres hypotheses sont alors emises et discutees. (auteur)

  16. Contribution to the study of {beta} disintegration and of nuclear structure using experiments on certain {beta}-{gamma} cascades: 198{sub Au}, 86{sub Rb}, 170{sub Tm}; Contribution a l'etude de la desintegration beta et a l'etude de la structure nucleaire a l'aide d'experiences sur certaines cascades beta-gamma: 198{sub Au}, 86{sub Rb}, 170{sub Tm}

    Energy Technology Data Exchange (ETDEWEB)

    Lachkar, J [Commissariat a l' Energie Atomique, Bruyeres-le-Chatel (France). Centre d' Etudes; Paris-11 Univ., fabulte des Sciences 91 - Orsay (France)

    1969-07-01

    {beta}{gamma} directional angular correlations and shapes of inner beta spectra leading to the first excited level of the final nucleus enable one to determine the nuclear matrix elements typical of the {beta} transition. In the three observed first forbidden cases: {sup 170}Tm, {sup 86}Rb, {sup 198}Au, these matrix elements do not confirm the independent shell model theory. Other hypotheses are then suggested and discussed. (author) [French] Les experiences de correlation angulaire {beta}{gamma} et l'etude du spectre {beta} conduisant au premier niveau excite du noyau final permettent de determiner les elements de matrices nucleaires caracteristiques de cette transition. Dans les trois cas etudies (transitions une fois interdites): {sup 170}Tm, {sup 86}Rb, {sup 198}Au, ces elements de matrices ne peuvent etre retrouves a l'aide du modele en couches et a particules independantes. D'autres hypotheses sont alors emises et discutees. (auteur)

  17. Study of gamma radiation between 0.1 and 1.0 MeV in the earth's atmosphere; Etude du rayonnement gamma entre 0,1 et 1 Mev dans l'atmosphere terrestre

    Energy Technology Data Exchange (ETDEWEB)

    Boclet, D [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-01-01

    The present work is devoted to some of the particular problems arising in the detection and localisation of sources of gamma radiation situated outside the earth's atmosphere. These weak sources can only be detected and localized if care is taken to eliminate gamma and particle radiations coming from other sources in the earth's atmosphere and in space. In order to separate the various sources of background noise, generally much stronger than the radiation under study, use is made of a directional detector whose characteristics are determined as described in the first part of the following report. The closest diffuse source considered is that constituted by the earth's atmosphere. Its detailed study will make it possible both to eliminate its effect when sources outside the earth are to be measured, and to predict the amount of secondary gamma radiation emitted by the same process in other celestial bodies, the moon in particular. This work considered in the 2. and 3. parts of the report. (author) [French] La presente etude est consacree a certains des problemes particuliers poses par la detection et la localisation des sources de rayonnement gamma situees hors de l'atmosphere terrestre. Ces sources faibles ne peuvent etre detectees et localisees que si l'on se protege des rayonnements gamma et particulaires provenant d'autres sources situees dans l'atmosphere terrestre et dans l'espace. Pour separer ces divers composants parasites, en general beaucoup plus intenses que le rayonnement a etudier, nous emploierons un detecteur directif dont nous determinons les caracteristiques dans la premiere partie de l'expose qui suit. La source diffuse la plus proche que nous considerons comme parasite est constituee par l'atmosphere terrestre. Son etude detaillee nous permettra d'une part de nous en proteger lorsque nous voudrons etudier les sources {gamma} extra-terrestres, d'autre part de prevoir le rayonnement gamma secondaire emis par le meme processus pour les autres corps

  18. Study of gamma radiation between 0.1 and 1.0 MeV in the earth's atmosphere; Etude du rayonnement gamma entre 0,1 et 1 Mev dans l'atmosphere terrestre

    Energy Technology Data Exchange (ETDEWEB)

    Boclet, D. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-01-01

    The present work is devoted to some of the particular problems arising in the detection and localisation of sources of gamma radiation situated outside the earth's atmosphere. These weak sources can only be detected and localized if care is taken to eliminate gamma and particle radiations coming from other sources in the earth's atmosphere and in space. In order to separate the various sources of background noise, generally much stronger than the radiation under study, use is made of a directional detector whose characteristics are determined as described in the first part of the following report. The closest diffuse source considered is that constituted by the earth's atmosphere. Its detailed study will make it possible both to eliminate its effect when sources outside the earth are to be measured, and to predict the amount of secondary gamma radiation emitted by the same process in other celestial bodies, the moon in particular. This work considered in the 2. and 3. parts of the report. (author) [French] La presente etude est consacree a certains des problemes particuliers poses par la detection et la localisation des sources de rayonnement gamma situees hors de l'atmosphere terrestre. Ces sources faibles ne peuvent etre detectees et localisees que si l'on se protege des rayonnements gamma et particulaires provenant d'autres sources situees dans l'atmosphere terrestre et dans l'espace. Pour separer ces divers composants parasites, en general beaucoup plus intenses que le rayonnement a etudier, nous emploierons un detecteur directif dont nous determinons les caracteristiques dans la premiere partie de l'expose qui suit. La source diffuse la plus proche que nous considerons comme parasite est constituee par l'atmosphere terrestre. Son etude detaillee nous permettra d'une part de nous en proteger lorsque nous voudrons etudier les sources {gamma} extra-terrestres, d'autre part de prevoir le rayonnement gamma

  19. Applications of prospecting geochemical techniques to the search for and to the study of uranium deposits in metropolitan France; Applications des techniques geochimiques de prospection a la recherche et a l'etude des gites uraniferes en France metropolitaine

    Energy Technology Data Exchange (ETDEWEB)

    Grimbert, Arnold

    1957-07-01

    After having recalled facts which leaded the CEA to use new geochemical techniques for the prospecting of uranium deposits through sampling and analysis of soils and waters, the author describes the organisation and methods implemented for this prospecting activity: team composition for sampling and analysis, role of each engineer and technician in the prospecting stages (preliminary study, routine prospecting, result interpretation), sampling and analysis processes. He also reports campaigns of geochemical prospecting: study of the La Chapelle Largeau deposit (objectives, geological context, preliminary study, routine prospecting, study of geochemical anomalies), tactical research on Verneix indices (study of radioactivity anomaly discovered by radio-prospecting), strategical searches in a non prospected area in the South of Avallon. The author discusses the issues of efficiency and cost price of this geochemical prospecting technique in soils and in waters. Appendices present the equipment and operation modality for soil sampling, and for soil sample preparation, and principles, equipment and products for soil analysis and for water analysis [French] A la suite des resultats satisfaisants obtenus dans la recherche de methodes de dosage adaptees au cas de l'uranium, la Direction des Recherches Minieres du Commissariat a l'Energie atomique a decide, en decembre 1954, d'utiliser, conjointement avec les methodes classiques de prospection, les techniques geochimiques pour la recherche et l'etude des gites uraniferes. Ces applications pratiques ont ete confiees a une Section de Geochimie dont l'organisation, les moyens en personnel et en materiel, ainsi que les methodes de travail, font l'objet d'un expose detaille. Quelques exemples de prospection, en France metropolitaine, montrent la nature des problemes poses (etude d'un gisement connu, recherche tactique sur des indices, recherche strategique dans une region non prospectee), les methodes utilisees pour les

  20. Study and achievement of a digital-analog-divider; Etude et realisation d'un diviseur-analogique-numerique

    Energy Technology Data Exchange (ETDEWEB)

    Petin, A [Commissariat a l' Energie Atomique, Cadarache (France). Centre d' Etudes Nucleaires

    1969-04-01

    This apparatus is designed to give directly, in digital form, the value of the ratio Vt1/V2 two analog voltages. It consists essentially of an analog-digital coder operating by successive weighing; the comparison voltage is made proportional to the divider V2 in the coder. The input dynamics are such that the voltages Vi and V2 are all in the range -50 mV to -5 V. Each of the circuits has an input impedance of about 10 K{omega}. As for the quotient, it is a binary number given in series and parallel form; it is made up of 8 bits, this giving a change of 1/16 to 16 per jump of 1/16 in the zone where the accuracy is highest (V2 {>=} 800 mV). The time required for a division is, at best, 15 {mu}sec. During the time of calculation, the voltages V{sub 1} and V{sub 2} should not vary by more than 1 per cent and 0.5 per cent respectively. The theory of the system and the investigation of a synoptic diagram, the study of the circuits and the actual construction are presented. (author) [French] Cet appareil est destine a fournir directement sous forme numerique la valeur du rapport V1/V2 de deux tensions analogiques. Il est constitue essentiellement d'un codeur analogique-numerique fonctionnant par pesees successives dans lequel la tension de reference est rendue proportionnelle au diviseur V2. La dynamique d'entree est telle que les tensions V1 et V2 peuvent etre comprises dans l'intervalle -50 mV a -5 V. Chacune des voies presente une impedance d'entree d'environ 10 K{omega}. En ce qui concerne le quotient, c'est un nombre binaire delivre sous les formes serie et parallele ; il est compose de 8 bits, ce qui donne une variation de 1/16 a 16 par bond de 1/16 dans la zone de meilleure precision (V2 {>=} 800 mV). Le temps necessaire pour effectuer la division est au mieux de 15 {mu}s. Durant le temps de calcul les tensions V{sub 1} et V{sub 2} ne doivent pas varier respectivement de plus de 1 pour cent et 0.5 pour cent. Apres avoir etabli la theorie du systeme, les

  1. Study and achievement of a digital-analog-divider; Etude et realisation d'un diviseur-analogique-numerique

    Energy Technology Data Exchange (ETDEWEB)

    Petin, A. [Commissariat a l' Energie Atomique, Cadarache (France). Centre d' Etudes Nucleaires

    1969-04-01

    This apparatus is designed to give directly, in digital form, the value of the ratio Vt1/V2 two analog voltages. It consists essentially of an analog-digital coder operating by successive weighing; the comparison voltage is made proportional to the divider V2 in the coder. The input dynamics are such that the voltages Vi and V2 are all in the range -50 mV to -5 V. Each of the circuits has an input impedance of about 10 K{omega}. As for the quotient, it is a binary number given in series and parallel form; it is made up of 8 bits, this giving a change of 1/16 to 16 per jump of 1/16 in the zone where the accuracy is highest (V2 {>=} 800 mV). The time required for a division is, at best, 15 {mu}sec. During the time of calculation, the voltages V{sub 1} and V{sub 2} should not vary by more than 1 per cent and 0.5 per cent respectively. The theory of the system and the investigation of a synoptic diagram, the study of the circuits and the actual construction are presented. (author) [French] Cet appareil est destine a fournir directement sous forme numerique la valeur du rapport V1/V2 de deux tensions analogiques. Il est constitue essentiellement d'un codeur analogique-numerique fonctionnant par pesees successives dans lequel la tension de reference est rendue proportionnelle au diviseur V2. La dynamique d'entree est telle que les tensions V1 et V2 peuvent etre comprises dans l'intervalle -50 mV a -5 V. Chacune des voies presente une impedance d'entree d'environ 10 K{omega}. En ce qui concerne le quotient, c'est un nombre binaire delivre sous les formes serie et parallele ; il est compose de 8 bits, ce qui donne une variation de 1/16 a 16 par bond de 1/16 dans la zone de meilleure precision (V2 {>=} 800 mV). Le temps necessaire pour effectuer la division est au mieux de 15 {mu}s. Durant le temps de calcul les tensions V{sub 1} et V{sub 2} ne doivent pas varier respectivement de plus de 1 pour cent et 0.5 pour cent. Apres avoir etabli la

  2. Study of the age of uranium-containing mineral deposits in the Limouzat, the bois-noir mountains (12963); Etude des ages des mineralisations uraniferes du gisement du Limouzat, Massif des bois-noirs (1963)

    Energy Technology Data Exchange (ETDEWEB)

    Durand, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1963-07-01

    The present work is concerned with 7 different samples taken at various levels in the Limouzat mine in the Bois-Noirs mountains. It has been possible to show that the uranium dates from 265 M.Y. and that a rearrangement occurred 65 M.Y. ago. A {gamma}-spectrometer study which was originally intended to show the existence of the lack of balance in the radon circulation, has made it possible to show that the {gamma} spectra recorded on various samples could be erroneous. We observed in effect that the presence of lead, iron, etc., had a strong influence on the {gamma} spectrum of the radium family, whereas all research workers have considered that concentrations in the uranium ore were negligible and had no significant effect on the study of the {gamma} spectra of the samples. It is obvious that an interesting study has to be undertaken on the screen effects of the different cations existing in the ores. We believe that it is possible to show the presence of certain elements directly by {gamma}-spectrometry. The ages measured with the mass spectrometer present two types of disagreement but these have been explained by considering that there occurred a first arrival of lead followed by a rearrangement and, at certain points, a second arrival at this date. Finally, the deposit studied undergoes a circulation of uranium and of radon. (author) [French] La presente etude a porte sur 7 prelevements differents effectues a divers niveaux de la mine du Limouzat, massif des Bois-Noirs. Elle a permis de mettre en evidence une premiere venue d'uranium il y a 265 M.A., suivie d'un remaniements il y a 65 M.A. Une etude au spectrometre {gamma} destinee, a l'origine, a prouver les desequilibres dus aux circulations de radon a permis de montrer que les spectres {gamma} enregistres sur divers echantillons pouvaient etre entaches d'erreurs. Nous nous sommes apercus en effet que la presence de plomb, de fer..., avait une forte influence sur le spectre {gamma} de la famille du radium

  3. Silver(I), Copper(I) and Copper(II) Complex of the New N,Se-Chelate Ligand 2-Phenylselenomethyl-1H-benzimidazole: Electrochemistry and Structure

    Czech Academy of Sciences Publication Activity Database

    Leboschka, M.; Sieger, M.; Sarkar, B.; Niemeyer, M.; Schurr, T.; Fiedler, Jan; Záliš, Stanislav; Kaim, W.

    2009-01-01

    Roč. 635, 6-7 (2009), s. 1001-1007 ISSN 0044-2313 R&D Projects: GA AV ČR KAN100400702; GA MŠk OC 139 Institutional research plan: CEZ:AV0Z40400503 Keywords : copper compounds * solid-state structures * electrochemistry * selenother ligand * silver complex Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.226, year: 2009

  4. 99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

    Science.gov (United States)

    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

  5. Generalities on the dynamic behaviour of rapid reactors. Preliminary studies on Rapsodie; Generalites sur le comportement dynamique des piles rapides. Etudes preliminaires de rapsodie

    Energy Technology Data Exchange (ETDEWEB)

    Campan, J L; Chaumont, J P; Clauzon, P P; Ghesquiere, G; Leduc, J; Schmitt, A P; Zaleski, C P [Commissariat a l' Energie Atomique, Cadarache (France). Centre d' Etudes Nucleaires

    1963-07-01

    The study of the dynamic behaviour of fast reactors may be divided into three section: 1. Stability studies around equilibrium power only the linear case was examining. S. Transient studies in the case of usual reactor operation (shut down, scram, etc.) with thermal shocks evaluation, for instance. 3. Explosion studies, for the maximum credible accidents. This report presents the status of the studies performed at the 'Physics Research Department' at Cadarache. Methods used are detailed and illustrated with the results obtained on a preliminary metallic core of the Rapsodie Reactor. (authors) [French] Le comportement dynamique des piles rapides, se presente tout naturellement sous trois aspects: 1. Etude de stabilite autour d'un regime d'equilibre (nous nous sommes bornes ici au cas lineaire). 2. Etude de regimes transitoires lors des operations normales de pile (arret, arret d'urgence, etc.) avec evaluation des chocs thermiques par exemple. 3. Etude des regimes transitoires de caractere explosif lors des accidents les plus graves possibles. Ce rapport presente l'etat des etudes a la date du 20 decembre 1961 a la Section d'Etudes de Piles Rapides a CADARACHE. Les methodes employees ont ete detaillees et illustrees a partir des resultats obtenus sur une premiere version 'combustible metallique' de Rapsodie. (auteurs)

  6. Etude cinétique de la dégradation de l'Endosufane en solution ...

    African Journals Online (AJOL)

    Etude cinétique de la dégradation de l'Endosufane en solution. S Traore, K Mamadou, A Dembele, V Yao, Y Bekro, P Mazellier, B Legube, P Houenou. Abstract. Les pesticides sont fréquemment utilisés en Côte d'Ivoire. Leur détection dans les eaux de forage témoigne de leur mauvais usage et d'un grave problème ...

  7. Study of the tributyl phosphate - 30% dodecane solvent; Etude du solvant phosphate tributylique - 30 % dodecane

    Energy Technology Data Exchange (ETDEWEB)

    Leroy, P [Commissariat a l' Energie Atomique, Fontenay-aux-Roses. Centre d' Etudes Nucleaires, 92 (France)

    1967-07-01

    This study, originating mainly from a literature survey, gives the principal chemical and physical features of the tributyl-phosphate (TBP) agent diluted at 30 volumes per cent in dodecane. The mixture is a very commonly used extractant in nuclear fuel processing. In this paper, the main following points are reported: -) the components (TBP and diluents) -) the TBP-diluents systems (non-loaded), -) the TBP-diluents-water systems, -) TBP-diluents-water-nitric acid systems, and -) industrial solvents. (author) [French] Cette etude, d'origine bibliographique, regroupe les caracteristiques physico-chimiques essentielles du phosphate tributylique (TBP) dilue a 30% en volume dans du dodecane. Ce melange constitue un agent d'extraction tres utilise dans le traitement des combustibles nucleaires. Les principaux points traites sont les suivants: -) les constituants (TBP et diluants), -) les systemes TBP-diluants non charges, -) les systemes TBP-diluants-eau, -) les systemes TBP-diluants-eau-acide nitrique, et -) les solvants industriels. (auteur)

  8. An economic study of the site of Marcoule; Etude economique du site de Marcoule

    Energy Technology Data Exchange (ETDEWEB)

    Duprat, H [Commissariat a l' Energie Atomique, Marcoule (France). Centre d' Etudes Nucleaires

    1964-07-01

    The study of this site of the Marcoule Center shows that its regional economical influence is limited to the buying power distributed among its personnel. This entails distortions between first this supplementary buying power and the overall markets within the possible Marcoule influence zone, and secondly the concentration on Bagnols-sur-Ceze and this town's normal extension possibilities. (author) [French] L'etude du site de Marcoule demontre que son influence economique se limite, pour la region, au pouvoir d'achat distribue a son personnel. Ceci entraine une disproportion d'une part entre ce pouvoir d'achat supplementaire et l'ensemble des marches contenus dans l'aire d'influence possible de Marcoule, d'autre part entre la concentration realisee a Bagnole-sur-Ceze et la capacite d'extension normale de cette agglomeration. (auteur)

  9. Neutronic study of the two french heavy water reactors; Etude neutronique des deux piles francaises a eau lourde

    Energy Technology Data Exchange (ETDEWEB)

    Horowitz, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1955-07-01

    The two french reactors - the reactor of Chatillon, named Zoe, and the reactor of Saclay - P2 - were the object of detailed neutronic studies which the main ideas are exposed in this report. These studies were mostly done by the Department of the Reactor Studies (D.E.P.). We have thus studied the distribution of neutronic fluxes; the factors influencing reactivity; the link between reactivity and divergence with the formula of Nordheim; the mean time life of neutrons; neutron spectra s of P2; the xenon effect; or the effect of the different adjustments of the plates and controls bar. (M.B.) [French] Les deux reacteurs francais - la pile de Chatillon, appelee ZOE, et la pile de Saclay, designee dans la suite par P2 - ont fait l'objet d'etudes neutroniques detaillees dont les principales sont exposees dans ce rapport. Ces etudes ont ete pour la plupart effectuees dans le cadre du Departement des Etudes de Piles (D.E.P.). Nous avons ainsi entre autre etudie la distribution du flux neutronique; les facteurs influencants la reactivite; le lien entre reactivite et divergence par la formule de Nordheim; le temps de vie moyen des neutrons; les spectres de neutrons de P2; l'effet xenon; ou encore l'effet des differents reglages des plaques et barres de controles. (M.B.)

  10. Studies of the Stabilization of Superconductor Coils; Etudes sur la Stabilisation des Bobines Supraconductrices

    Energy Technology Data Exchange (ETDEWEB)

    Donadieu, L.; Maldy, J. [Compagnie Generale d' Electricite Marcoussis (France)

    1966-12-15

    operation of the coil will be stable and the passage of the I-B characteristic of the material will be reversible; (b) Ic < Im, the operation of the coil is unstable and any sufficiently large disturbances (flux jump, movement of windings, etc. ) can produce blocking. This is inevitably the case with the large coils whose operational limit tends towards Im. Different coils have been constructed with more or leas stabilised materials and the results of tests on them are analysed as a' function of the previous theories. There Is a full discussion of the advantages and disadvantages of coil stabilizations. (author) [French] La stabilisation de l'intensite du courant dans les bobinages supra-conducteurs, qui apparait d'une importance capitale pour la construction de bobinages de grande taille , est etudiee a la fois du point de vue theorique et du point de vue experiment a l. L'etude de la dynamique de la transition d'un supraconducteur transportant du courant, entre l ' e t at supraconducteur a resistance nulle et l ' e tat a resistance normale ( l e blocage), revele l'existence d'une intensite caracteristique, Im, pour laquelle la vitesse de propagation de la region normale est nulle. Cette intensite depend directement des echanges de chaleur entre le supraconducteur et le milieu ambiant, et de la resistance du materiau a l ' e t a t normal; Im depend indirectement de l'intensite du champ magnetique. Si un supraconducteur est utilise avec une intensite de courant inferieure a Im, la vitesse de propagation est negative et le supraconducteur est capable eventuellement de realiser la transition inverse de l ' e t a t normal a l ' e t a t supraconducteur. On peut montrer que pour une intensite Is telle que Is = Im/ Square-Root 2 , la vitesse de propagation qui est negative devient infiniment grande. L'existence de ces 2 intensites caracteristiques permet de distinguer trois cas de comportement differents selon l'intensite du courant qui parcourt le supraconducteur. L'auteur a

  11. Photophysics and electrochemistry relevant to photocatalytic water splitting involved at solid–electrolyte interfaces

    KAUST Repository

    Shinagawa, Tatsuya; Cao, Zhen; Cavallo, Luigi; Takanabe, Kazuhiro

    2016-01-01

    Direct photon to chemical energy conversion using semiconductor-electrocatalyst-electrolyte interfaces has been extensively investigated for more than a half century. Many studies have focused on screening materials for efficient photocatalysis

  12. Impact of Soil Composition and Electrochemistry on Corrosion of Rock-cut Slope Nets along Railway Lines in China

    Science.gov (United States)

    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.

  13. Morphologic, magnetic, and Moessbauer spectral properties of Fe75Co25 nanoparticles prepared by ultrasound-assisted electrochemistry

    International Nuclear Information System (INIS)

    Mancier, Valerie; Delplancke, J.-L.; Delwiche, Jacques; Hubin-Franskin, M.-J.; Piquer, Cristina; Rebbouh, Leila; Grandjean, Fernande

    2004-01-01

    Nanopowders of Fe 75 Co 25 alloys have been prepared by ultrasound-assisted electrochemistry. Their composition, crystallographic structure, morphology, have been studied by X-ray diffraction, transmission electron microscopy, X-ray fluorescence, and high-energy electron diffraction. The nanopowders are found to present a composition well determined by the electrolyte bath composition, they show a bcc structure. The iron and cobalt atoms exhibit a very homogeneous distribution in the particles. The magnetic properties of the nanopowders have been measured between 5 and 295 K with a vibrating sample magnetometer and their Moessbauer spectra have been obtained at 295 K. The saturation magnetization is characteristic of FeCo alloys. The magnetic behavior and transmission electron microscopy observations of the particles indicate strongly interacting particles with a radius of ca. 2-4 nm, particles which may form agglomerates of larger size. The measured average hyperfine field is situated at the maximum of the Slater-Pauling curve for the FeCo alloys

  14. Observation of nanometer-sized electro-active defects in insulating layers by fluorescence microscopy and electrochemistry.

    Science.gov (United States)

    Renault, Christophe; Marchuk, Kyle; Ahn, Hyun S; Titus, Eric J; Kim, Jiyeon; Willets, Katherine A; Bard, Allen J

    2015-06-02

    We report a method to study electro-active defects in passivated electrodes. This method couples fluorescence microscopy and electrochemistry to localize and size electro-active defects. The method was validated by comparison with a scanning probe technique, scanning electrochemical microscopy. We used our method for studying electro-active defects in thin TiO2 layers electrodeposited on 25 μm diameter Pt ultramicroelectrodes (UMEs). The permeability of the TiO2 layer was estimated by measuring the oxidation of ferrocenemethanol at the UME. Blocking of current ranging from 91.4 to 99.8% was achieved. Electro-active defects with an average radius ranging between 9 and 90 nm were observed in these TiO2 blocking layers. The distribution of electro-active defects over the TiO2 layer is highly inhomogeneous and the number of electro-active defect increases for lower degree of current blocking. The interest of the proposed technique is the possibility to quickly (less than 15 min) image samples as large as several hundreds of μm(2) while being able to detect electro-active defects of only a few tens of nm in radius.

  15. Ubiquinol-cytochrome c reductase (Complex III) electrochemistry at multi-walled carbon nanotubes/Nafion modified glassy carbon electrodes

    International Nuclear Information System (INIS)

    Pelster, Lindsey N.; Minteer, Shelley D.

    2012-01-01

    Highlights: ► The electron transport chain is important to the understanding of metabolism in the living cell. ► Ubiquinol-cytochrome c reductase is a membrane bound complex of the electron transport chain (Complex III). ► The paper details the first bioelectrochemical characterization of ubiquinol-cytochrome c reductase at an electrode. - Abstract: Electron transport chain complexes are critical to metabolism in living cells. Ubiquinol-cytochrome c reductase (Complex III) is responsible for carrying electrons from ubiquinol to cytochrome c, but the complex has not been evaluated electrochemically. This work details the bioelectrochemistry of ubiquinol-cytochrome c reductase of the electron transport chain of tuber mitochondria. The characterization of the electrochemistry of this enzyme is investigated in carboxylated multi-walled carbon nanotube/tetrabutyl ammonium bromide-modified Nafion ® modified glassy carbon electrodes by cyclic voltammetry. Increasing concentrations of cytochrome c result in a catalytic response from the active enzyme in the nanotube sandwich. The experiments show that the enzyme followed Michaelis–Menten kinetics with a K m for the immobilized enzyme of 2.97 (±0.11) × 10 −6 M and a V max of 6.31 (±0.82) × 10 −3 μmol min −1 at the electrode, but the K m and V max values decreased compared to the free enzyme in solution, which is expected for immobilized redox proteins. This is the first evidence of ubiquinol-cytochrome c reductase bioelectrocatalysis.

  16. Impact of Soil Composition and Electrochemistry on Corrosion of Rock-cut Slope Nets along Railway Lines in China.

    Science.gov (United States)

    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.

  17. Forensic analyses of explosion debris from the January 2, 1992 Pd/D2O electrochemistry incident at SRI International

    International Nuclear Information System (INIS)

    Andresen, B.; Whipple, R.; Vandervoort, D.; Grant, P.

    1992-01-01

    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

  18. Electrochemistry and determination of epinephrine using a mesoporous Al-incorporated SiO{sub 2} modified electrode

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Yanhong; Yang, Jinquan; Wu, Kangbing [Department of Chemistry, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2008-05-30

    The potential application of Al-incorporated mesoporous SiO{sub 2} (denoted as Al-MCM-41) in electrochemistry as a novel electrode material was investigated. The peak currents of K{sub 3}[Fe(CN){sub 6}] remarkably increase and the peak potential separation obviously decreases at the mesoporous Al-MCM-41 modified carbon paste electrode (CPE). These phenomena suggest that the mesoporous Al-MCM-41 modified CPE possesses larger electrode area and electron transfer rate constant. Furthermore, the electrochemical behavior of epinephrine (EP) was investigated in different supporting electrolytes such as 0.01 mol L{sup -1} HClO{sub 4} and pH 7.0 phosphate buffer. It is found that the mesoporous Al-MCM-41 modified CPE exhibits catalytic ability to the oxidation of EP due to remarkable peak current enhancement and negative shift of peak potential. The electrochemical oxidation mechanism was also discussed. Finally, a novel electrochemical method was proposed for the determination of EP, which used to determine EP in urine samples. (author)

  19. Electrochemistry and determination of epinephrine using a mesoporous Al-incorporated SiO{sub 2} modified electrode

    Energy Technology Data Exchange (ETDEWEB)

    Zeng Yanhong; Yang Jinquan [Department of Chemistry, Huazhong University of Science and Technology, Wuhan 430074 (China); Wu Kangbing [Department of Chemistry, Huazhong University of Science and Technology, Wuhan 430074 (China)], E-mail: kbwu@mail.hust.edu.cn

    2008-05-30

    The potential application of Al-incorporated mesoporous SiO{sub 2} (denoted as Al-MCM-41) in electrochemistry as a novel electrode material was investigated. The peak currents of K{sub 3}[Fe(CN){sub 6}] remarkably increase and the peak potential separation obviously decreases at the mesoporous Al-MCM-41 modified carbon paste electrode (CPE). These phenomena suggest that the mesoporous Al-MCM-41 modified CPE possesses larger electrode area and electron transfer rate constant. Furthermore, the electrochemical behavior of epinephrine (EP) was investigated in different supporting electrolytes such as 0.01 mol L{sup -1} HClO{sub 4} and pH 7.0 phosphate buffer. It is found that the mesoporous Al-MCM-41 modified CPE exhibits catalytic ability to the oxidation of EP due to remarkable peak current enhancement and negative shift of peak potential. The electrochemical oxidation mechanism was also discussed. Finally, a novel electrochemical method was proposed for the determination of EP, which used to determine EP in urine samples.

  20. Interconnection of Key Microbial Functional Genes for Enhanced Benzo[a]pyrene Biodegradation in Sediments by Microbial Electrochemistry.

    Science.gov (United States)

    Yan, Zaisheng; He, Yuhong; Cai, Haiyuan; Van Nostrand, Joy D; He, Zhili; Zhou, Jizhong; Krumholz, Lee R; Jiang, He-Long

    2017-08-01

    Sediment microbial fuel cells (SMFCs) can stimulate the degradation of polycyclic aromatic hydrocarbons in sediments, but the mechanism of this process is poorly understood at the microbial functional gene level. Here, the use of SMFC resulted in 92% benzo[a]pyrene (BaP) removal over 970 days relative to 54% in the controls. Sediment functions, microbial community structure, and network interactions were dramatically altered by the SMFC employment. Functional gene analysis showed that c-type cytochrome genes for electron transfer, aromatic degradation genes, and extracellular ligninolytic enzymes involved in lignin degradation were significantly enriched in bulk sediments during SMFC operation. Correspondingly, chemical analysis of the system showed that these genetic changes resulted in increases in the levels of easily oxidizable organic carbon and humic acids which may have resulted in increased BaP bioavailability and increased degradation rates. Tracking microbial functional genes and corresponding organic matter responses should aid mechanistic understanding of BaP enhanced biodegradation by microbial electrochemistry and development of sustainable bioremediation strategies.

  1. Using porphyrin-amino acid pairs to model the electrochemistry of heme proteins: experimental and theoretical investigations.

    Science.gov (United States)

    Samajdar, Rudra N; Manogaran, Dhivya; Yashonath, S; Bhattacharyya, Aninda J

    2018-04-18

    Quasi reversibility in electrochemical cycling between different oxidation states of iron is an often seen characteristic of iron containing heme proteins that bind dioxygen. Surprisingly, the system becomes fully reversible in the bare iron-porphyrin complex: hemin. This leads to the speculation that the polypeptide bulk (globin) around the iron-porphyrin active site in these heme proteins is probably responsible for the electrochemical quasi reversibility. To understand the effect of such polypeptide bulk on iron-porphyrin, we study the interaction of specific amino acids with the hemin center in solution. We choose three representative amino acids-histidine (a well-known iron coordinator in bio-inorganic systems), tryptophan (a well-known fluoroprobe for proteins), and cysteine (a redox-active organic molecule). The interactions of these amino acids with hemin are studied using electrochemistry, spectroscopy, and density functional theory. The results indicate that among these three, the interaction of histidine with the iron center is strongest. Further, histidine maintains the electrochemical reversibility of iron. On the other hand, tryptophan and cysteine interact weakly with the iron center but disturb the electrochemical reversibility by contributing their own redox active processes to the system. Put together, this study attempts to understand the molecular interactions that can control electrochemical reversibility in heme proteins. The results obtained here from the three representative amino acids can be scaled up to build a heme-amino acid interaction database that may predict the electrochemical properties of any protein with a defined polypeptide sequence.

  2. A multi-site array for combined local electrochemistry and electrophysiology in the non-human primate brain.

    Science.gov (United States)

    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 (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.

  3. Etude des phenomenes dynamiques ultrarapides et des caracteristiques impulsionnelles d'emission terahertz du supraconducteur YBCO

    Science.gov (United States)

    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

  4. Theoretical and Experimental Studies of High-Frequency Plasma Structures; Etudes Theoriques et Experimentales sur les Structures HF a Plasma

    Energy Technology Data Exchange (ETDEWEB)

    Consoli, T. [CEA, Centre d' Etudes Nucleaires de Saclay (France)

    1969-03-15

    currents of more than 20 keV and of about 10 mA/cm{sub 2} were obtained. Ion entrainment for a magnetic field twice that necessary for resonance was also verified. Finally, with the Pleiade I device ({lambda} = 100 cm, P{sub HF} {approx}500 W, CW), the reflection of accelerated plasma jets by a mirror pulse lasting 75 {mu}s was verified. From measurements of the fast neutrals resulting from ion charge exchange (with the residual gas; p {<=} 10{sup -4} mmHg) it was deduced that the density of the ions (directed energy {approx} 1.5 keV) may be increased from 2 x 10{sub 8} cm{sup -3} (direct beam) to 6 x 10{sup 9} cm{sup -3} during the mirror pulse. The accumulated density appears to be limited by the charge exchange, and the increased duration of the mirror pulse to 200 {mu}s with p Less-Than-Or-Equivalent-To 10{sup -4} mmHg (unchanged) hardly improves the accumulation ratio. This agrees with the predictions if one takes into account the fact that the ion lifetime is {approx} 10 {mu}s. (author) [French] Il s'agit des etudes sur les structures HF a la resonance ( {omega}{sub ec} = {omega}{sub HF}) en champ magnetique inhomogene. Les points suivants ont ete developpes theoriquement: description analytique complete (relativiste et non lineaire) du mouvement individuel, compte tenu du fait que le nombre de revolutions des particules dans la zone de resonance est eleve ; etude du champ de charge d' espace autocoherent ( 'self-consistent') en vue d'etablir les conditions pour que l' energie des ions soit de l'ordre de celle gagnee par les electrons dans la zone de resonance; calcul du champ HF autocoherent dans le plasma accelere en vue d' etablir les conditions de fonctionnement optimum de l'accelerateur HF; probleme des pertes aux miroirs. Les resultats experimentaux ont ete obtenus avec divers dispositifs construits en vue de la verification des previsions theoriques.

  5. Investigation of Streptococcus mutans biofilm growth on modified Au(111)-surfaces using AFM and electrochemistry

    DEFF Research Database (Denmark)

    Hu, Yifan; Zhang, Jingdong; Ulstrup, Jens

    2011-01-01

    Biofilms of the bacterium Streptococcus mutans constitute perhaps the most important direct cause of human dental caries formation. We have studied S. mutans biofilm formation and properties on Au(111)-surfaces modified by self-assembled molecular monolayers (SAMs) of different thiol-based molecu...

  6. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

    International Nuclear Information System (INIS)

    Sundararaman, Ravishankar; Goddard, William A. III; Arias, Tomas A.

    2017-01-01

    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. 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.

  7. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

    Science.gov (United States)

    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.

  8. Reduced Graphene Oxide: Is it a promising catalyst for the electrochemistry of [UO2(CO3)3]4−/[UO2(CO3)3]5−?

    International Nuclear Information System (INIS)

    Guin, Saurav K.; Ambolikar, Arvind S.; Kamat, J.V.

    2015-01-01

    Highlights: • First report on aqueous electrochemistry of uranium on graphene materials. • Graphene(Nafion)/GC did not show applicability for the anionic analytes. • Electrochemically Reduced Graphene Oxide (ERGNO) was synthesised by cyclic voltammetry. • ERGNO catalysed the electrochemistry of [U VI O 2 (CO 3 ) 3 ] 4- /[U V O 2 (CO 3 ) 3 ] 5- . • Both the cathodic and anodic overpotentials of U(VI)/U(V) reaction decreased on ERGNO. - Abstract: The graphene has been emerging in the electrocatalysis and electroanalysis as the potent surface modifying agents for the working electrodes. However, the aqueous electrochemistry of the actinides on graphene (or graphene type materials) is yet unexplored. In this paper, the aqueous electrochemistry of [U VI O 2 (CO 3 ) 3 ] 4− /[U V O 2 (CO 3 ) 3 ] 5− redox couple was systematically investigated on electrochemically reduced graphene oxide (ERGNO) modified glassy carbon (GC) electrode in saturated Na 2 CO 3 solution (pH ∼12.3). This is the first report on aqueous actinide electrochemistry on graphene materials. The results showed that ERGNO could catalyse the redox chemistry of [U VI O 2 (CO 3 ) 3 ] 4− /[U V O 2 (CO 3 ) 3 ] 5− by reducing both the cathodic and anodic overpotentials compared to bare GC electrode. However, no enhancement in the peak current was observed on ERGNO electrode for the same reaction. Therefore, the present study introduces an appeal for a systematic investigation on the electrochemistry of the actinides at graphene materials to gear up their applications in nuclear technology

  9. Electrochemistry of actinide on electrochemically reduced graphene oxide: Electrocatalysis of Np(VI)O22+/Np(V)O2+ in nitric acid solution

    International Nuclear Information System (INIS)

    Ambolikar, Arvind S.; Guin, Saurav K.; Kasar, U.M.; Kamat, J.V.

    2015-01-01

    Highlights: • First report of aqueous electrochemistry of neptunium on electrochemically reduced graphene oxide (ERGNO). • First report on the electrochemical impedance spectroscopy of Np (VI) O 2 2+ /Np (V) O 2 + . • The electrochemical reversibility of Np (VI) O 2 2+ /Np (V) O 2 + redox couple improves on ERGNO compared to GC. • ERGNO shows higher sensitivity for the determination of Np compared to bare GC electrode. • The efficiency of detection of Np by ERGNO is improved by virtue of the electrocatalysis. - Abstract: Driven by the academic interest, we have studied the aqueous electrochemistry of neptunium (Np) in 1 M nitric acid solution on the electrochemically reduced graphene oxide (ERGNO) modified glassy carbon (GC) electrode. Similar to our previous experiences on the electrocatalytic action of ERGNO on the electrochemistry of uranium(VI)/uranium(IV) and plutonium(IV)/plutonium(III) redox couples, the present study confirms the robust electrocatalytic ability of ERGNO for the redox reaction of Np (VI) O 2 2+ /Np (V) O 2 + in acidic solution even at high anodic working potentials. The extent of the electrochemical reversibility of Np (VI) O 2 2+ /Np (V) O 2 + redox couple increases on ERGNO compared to the bare GC electrode. For the first time, the electron transfer reaction of Np (VI) O 2 2+ /Np (V) O 2 + redox couple is investigated by electrochemical impedance spectroscopy. The improved sensitivity as well as the lower limit of detection of Np by anodic square wave voltammetry on ERGNO compared to bare GC opens up the application of ERGNO in the nuclear science and technology.

  10. Tuning the electrochemistry of homoleptic cobalt 4,4′-disubstituted-2,2′-bipyridine redox mediators

    International Nuclear Information System (INIS)

    Nolan, Jesse P.; Jones, Timothy W.; Donne, Scott W.; Wilson, Gregory J.

    2013-01-01

    Highlights: • Cobalt(II) tris(2,2′-bipyridine) complexes were prepared with electron withdrawing or donating groups in the ligand 4 and 4′ positions. • The formal potential of the redox couples was tuned with the Hammett Parameter of the substituent. • Substitution also leads to sluggish oxidation kinetics, as observed with decreased heterogeneous rate constant and transfer coefficient >0.5. Reduction kinetics remained facile. -- Abstract: The electrochemistry of a series of Co(II) tris(4,4′-disubstituted-2,2′-bipyridine) hexafluorophosphate complexes was investigated in acetonitrile, and compared to the parent, un-substituted 2,2′-bipyridine complex. The introduction of an electron-withdrawing halogen substituent increased the formal redox potential of the couple by 190–270 mV, in the order of F > Cl > Br > I. Substitution with electron-donating tert-butyl and methoxy groups acted as electron donating groups, and decreased the formal potential by 150–190 mV. Substitution in the 4,4′ positions, irrespective of electron withdrawing or donating character, also imparted an asymmetry in the anodic peak in the cyclic voltammograms, where the oxidation process became more sluggish than the corresponding reduction. Kinetics of Co(II) oxidation was evaluated by Koutecký–Levich analysis at a rotating Pt disc, revealing superior oxidation kinetics of the un-substituted 2,2′-bipyridine complex by up to an order of magnitude or larger. The anodic transfer coefficients were also extracted from this analysis, revealing ideal α = 0.50 for the parent complex, to 0.70 ≤ α ≤ 0.88 for complexes with substituted ligands

  11. Analysis of gases by a pulsed voltammetric sensor and the electrochemistry of high T[sub c] superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Rochani, S.

    1991-01-01

    This thesis is presented in two parts: Studies of gas sensing probes and the electrochemistry of superconductors. A Clark type polarographic oxygen sensor was used to analyze oxygen, hydrogen, chlorine, sulphur dioxide and nitrogen dioxide. A pulsed potential was applied driven by an IBM/XT compatible microcomputer with a 12 bit A-D/D-A card. In a series of experiments for each gas singly, and then mixtures, the probe was calibrated at different concentrations of gas dissolved in water at different times during the pulse to observe the optimum measurement. In the case of oxygen for a 20 s pulse at [minus]0.65 V between a platinum and silver/silver chloride, the optimum calibration was obtained between 2 and 4 s with a detection limit of 0.27 ppm oxygen. Hydrogen was determined at +0.60 V with a 50 s pulse and optimum range 3 to 4 s and detection limit 0.02 ppm. Chlorine was reduced at 0 V and optimally detected after 2 s of a 20 s pulse with a detection limit of 3 ppm. A mixture of hydrogen and oxygen was analyzed without mutual interference by a train of pulses at [minus]0.65, 0, +0.60 V or [minus]0.65, +0.60 V. For sulphur dioxide, a new probe was constructed with a separate reference, working and auxillary electrodes to overcome the formation of silver sulphide at the auxillary electrode. A preliminary study of nitrogen dioxide was done by observing the oxidation and reduction current at different applied voltages. Samples of each of the room temperature superconductors YBa[sub 2]Cu[sub 3]O[sub 7[minus][sigma

  12. Different behaviors of single and multi wall carbon nanotubes for studying electrochemistry and electrocatalysis of choline oxidase

    International Nuclear Information System (INIS)

    Sajjadi, Sharareh; Ghourchian, Hedayatollah; Rahimi, Parvaneh

    2011-01-01

    Highlights: → In the presence of a typical room temperature ionic liquid (RTIL), Choline oxidase (ChOx) as a model enzyme was uniformly immobilized on either single or multi wall carbon nanotubes (SWCNTs or MWCNTs) covered on glassy carbon (GC) electrode, and the electron transfer and electroanalytical response of enzyme toward choline was evaluated. → ChOx on RTIL/MWCNTs/GC electrode showed higher electrical conductivity, better reversibility of redox reaction and higher electron transfer rate indicating more facile and rapid rate of electron transfer. → On the other hand, RTIL/SWCNTs/GC electrode showed higher amount of enzyme loading, higher enzyme-substrate affinity, lower detection limit, better sensitivity and wider linear range. → Consequently, MWCNTs are preferable for kinetic study of ChOx, while SWCNTs are more convenient for biosensing applications. - Abstract: This work presents a detailed comparison between single and multi wall carbon nanotubes (SWCNTs and MWCNTs) in an effort to understand which could be a better supporting material for studying the electrochemistry and electrocatalysis of enzymes. Choline oxidase (ChOx) was chosen as a model enzyme for evaluation of the electrodes' performance. The enzyme was adsorbed on either SWCNT or MWCNT modified electrode, in the presence of a typical room temperature ionic liquid (RTIL), and its electron transfer and electroanalytical response toward choline was investigated. RTIL/MWCNTs/GC electrode was uniformly covered by ChOx. Besides, higher electrical conductivity, better reversibility of the ChOx redox reaction and higher electron transfer rate of the enzyme indicated more facile and rapid rate of electron transfer. On the other hand, RTIL/SWCNTs/GC electrodes showed higher amount of enzyme loading, higher enzyme-substrate affinity, lower detection limit, better sensitivity and wider linear range. Consequently, MWCNTs are preferable for kinetic study of ChOx, while SWCNTs are more convenient

  13. Silver vanadium diphosphate Ag2VP2O8: Electrochemistry and characterization of reduced material providing mechanistic insights

    International Nuclear Information System (INIS)

    Takeuchi, Esther S.; Lee, Chia-Ying; Cheng, Po-Jen; Menard, Melissa C.; Marschilok, Amy C.; Takeuchi, Kenneth J.

    2013-01-01

    Silver vanadium phosphorous oxides (Ag w V x P y O z ) 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, Ag 2 VP 2 O 8 , where the structural differences associated with phosphorous oxides versus diphosphates profoundly affect the associated electrochemistry. Reminiscent of Ag 2 VO 2 PO 4 reduction, in-situ formation of silver metal nanoparticles was observed with reduction of Ag 2 VP 2 O 8 . However, counter to Ag 2 VO 2 PO 4 reduction, Ag 2 VP 2 O 8 demonstrates a significant decrease in conductivity upon continued electrochemical reduction. Structural analysis contrasting the crystallography of the parent Ag 2 VP 2 O 8 with that of the proposed Li 2 VP 2 O 8 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 Ag 2 VP 2 O 8 materials, which bodes well for enhanced safety of batteries incorporating this material. - Graphical abstract: Structure and galvanostatic intermittent titration-type test data for silver vanadium diphosphate, Ag 2 VP 2 O 8 . Highlights: ► First electrochemical study of a silver vanadium diphosphate, Ag 2 VP 2 O 8 . ► In-situ formation of Ag 0 nanoparticles was observed upon electrochemical reduction. ► Structural analysis used to provide insight of the electrochemical behavior

  14. Surface analysis and electrochemistry of a robust carbon-nanofiber-based electrode platform H_2O_2 sensor

    International Nuclear Information System (INIS)

    Suazo-Dávila, D.; Rivera-Meléndez, J.; Koehne, J.; Meyyappan, M.; Cabrera, C.R.

    2016-01-01

    Highlights: • Vertically aligned carbon nanofibers were intercalated with SiO_2 for mechanical strength and isolation of individual electrodes. • Stable and robust electrochemical hydrogen peroxide sensor is stable and robust. • Five consecutive calibration curves were done with different hydrogen peroxide concentrations over a period of 3 days without any deterioration in the electrochemical response. • The sensor was also used for the measurement of hydrogen peroxide as one of the by-products of the reaction of cholesterol oxidase with cholesterol and the sensor response exhibited linear behavior from 50 μM to 1 mM in cholesterol concentration. • In general, the electrochemical sensor is robust, stable, and reproducible, and the detection limit and sensitivity responses were among the best when compared with the literature. - Abstract: 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.

  15. Fully solar-driven thermo- and electrochemistry for advanced oxidation processes (STEP-AOPs) of 2-nitrophenol wastewater.

    Science.gov (United States)

    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.

  16. Etudes physiques des mélanges eau-cryoprotecteurs

    Science.gov (United States)

    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

  17. Contribution to the study of french pitchblendes; Contribution a l'etude des pechblendes francaises

    Energy Technology Data Exchange (ETDEWEB)

    Geffroy, J [Commissariat a l' Energie Atomique, Lab. de Mineralogie, Centre de Chatillon (France). Centre d' Etudes Nucleaires; Sarcia, J A [Commissariat a l' Energie Atomique, Div. de la Crouzille, Haute Vienne (France). Centre d' Etudes Nucleaires

    1955-07-01

    The authors first review the characteristics of uraninite-pitchblende, as deduced of present literature. They set apart from typical pitchblende a black oxide aspect, which probably corresponds to neo-formations, and a 'para-pitchblende' aspect, which they relate to deep sur-oxidation of normal pitchblende. They insist on the easy replacement of pitchblende by silica. and give indications as to changes in vein stones (fluorite, quartz, etc...). A detailed study of paragenesis and successions in french uranium districts follows (including discussion of uranium of uranium-bearing coals). The authors attempt to classify french pitchblende veins. They are chiefly epithermal and poor in satellite ores. Three types of deposits are identified: massive - pitchblende type, silica type, fluorite type. These deposits, as those of Portugal, are included in granite, Central-European peri-batholitic types where uranium associates which Ni, Co, Bi and Ag, are in France both rare and poor. Finally, the authors attempt to bring out in the european Hercynian area a particular distribution of paragenetic types. (authors) [French] Les auteurs recapitulent d'abord les caracteres et les occurences de l'uraninite - pechblende, tels qu'ils peuvent etre degages de l'actuelle bibliographie. Ils exposent ensuite les faits qui du point de vue mineralogique seulement ressortent de l'etude mineralogique et chalcographique des pechblendes francaises et de leurs satellites. Ils distinguent de la pechblende-type un facies oxyde noir; correspondant probablement a une neoformation, et un facies parapechblende, qui est rapporte a une sur oxydation hypogene de la pechblende proprement dite. Ils insistent sur le facile remaniement de la pechblende par la slice; et donnent quelques precisions sur les modifications des gangues (fluorine, quartz, etc...). Suit l'etude detaillee des parageneses et des successions dans les districts uraniferes francais: Divisions du Limousin, de Grury, de Lachaux et de

  18. Study of some properties of zirconium phosphate; Etude de quelques proprietes du phosphate de zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Prospert, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1963-05-01

    Zirconium phosphate has been studied with a view to using it as an ion exchanger: the first objective was to develop a method of preparation easy to apply and also reproducible. To this end, several tests were carried out varying the molar ratios of phosphorus and of zirconium. Some physical properties such as the diffraction of X-rays were examined. The work then involved certain chemical properties, particularly the percentages of free water and structural water given by the loss on calcination, the Karl-Fisher method and the weight losses by thermogravimetry. Finally an attempts was made to apply the exchanger to the separation of alkaline ions. The static tests showed that the order of fixation of these ions was Cs{sup +} > Rb{sup +} >> K{sup +} > Na{sup +}. Tests with columns showed that Na{sup +} and K{sup +} were easily separable, as was the Rb{sup +}-Cs{sup +} mixture, this last pair being fairly difficult to dissociate. (author) [French] Le phosphate de zirconium a ete etudie en vue de son utilisation comme echangeur d'ions: le premier but a atteindre a ete de mettre au point une preparation pouvant se reveler facilement utilisable ainsi qu'aisement reproductible. A cet effet, plusieurs essais ont ete effectues en faisant varier les rapports molaires du phosphore et du zirconium. Quelques proprietes physiques, telle la diffraction des rayons X, ont ete abordees. Ensuite, l'etude a porte sur certaines proprietes chimiques, particulierement les pourcentages d'eau libre et d'eau de structure par des pertes au feu, utilisation de la methode de Karl-Fisher, ainsi que des pertes de poids a la thenmobalance. Enfin, on a tente d'utiliser l'echangeur a la separation des ions alcalins. Les etudes statiques ont permis de constater que l'ordre de fixation de ces ions etait Cs{sup +} > Rb{sup +} >> K{sup +} > Na{sup +}. Les essais effectues en colonne ont montre que Na{sup +} et K{sup +} etaient aisement separables entre eux, ainsi que du couple Rb{sup +}-Cs{sup +}, ce

  19. Study of points defects produced by irradiation of monocrystalline nickel and polycrystalline gadolinium; Etude des defauts ponctuels crees par irradiation dans: - le nickel monocristallin - le gadolinium polycristallin

    Energy Technology Data Exchange (ETDEWEB)

    Cope, R [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    The work described in this thesis falls into two parts: the first comprises a study of magnetocrystalline nickel by resistivity measurements; the second is a description of resistivity and magnetic after effect measurements on an h.c.p. ferromagnetic crystal other than cobalt, namely gadolinium. For the first part we have demonstrated the existence of a small but definite orientation dependence in the creation of point defects by electron irradiation (20 deg. K) of a nickel single crystal. In particular, the effect is manifested in the form of the stage I{sub C}, II and III in the resistivity recovery. In the second part an important result has emerged: namely that there is no magnetic after effect phenomenon in a neutron irradiated (27 deg. K) ferromagnetic metal. Several considerations are discussed by way of a preliminary interpretation of this important difference between gadolinium and cobalt. (author) [French] Le travail qui a fait l'objet de ce memoire comporte deux parties distinctes: une premiere constituee de l'etude du nickel sous la forme de monocristaux, a l'aide de mesures de resistivite; la seconde partie est composee d'experiences de resistivite et de trainage magnetique sur un cristal h.c.p. ferromagnetique autre que le cobalt, le gadolinium. Dans la premiere partie, nous avons mis en evidence un effet sensible de la direction de l'irradiation electronique (a 20 deg. K) sur la creation des defauts ponctuels dans le nickel monocristallin, en particulier au niveau des stades I{sub C}, II et III des courbes de revenu de la resistivite. Dans la deuxieme partie, un point particulier a ete mis en evidence: l'absence de phenomene de trainage magnetique dans un metal ferromagnetique irradie par des neutrons (a 27 deg. K). Quelques points d'interpretations preliminaires sont avances pour expliquer la difference notable entre le gadolinium et le cobalt. (auteur)

  20. Electrochemistry and biosensing activity of cytochrome c immobilized on a mesoporous interface assembled from carbon nanospheres

    International Nuclear Information System (INIS)

    Wang, Y.; Bian, X.; Liao, L.; Zhu, J.; Guo, K.; Kong, J.; Liu, B.

    2012-01-01

    We report on an amperometric biosensor for hydrogen peroxide. It is obtained via layer-by-layer assembly of ordered mesoporous carbon nanospheres and poly(diallyldimethylammonium) on the surface of an indium tin oxide (ITO) glass electrode and subsequent adsorption of cytochrome c. UV-vis absorption spectroscopy was applied to characterize the process of forming the assembled layers. Cyclic voltammetry revealed a direct and quasi-reversible electron transfer between cytochrome c and the surface of the modified ITO electrode. The surface-controlled electron transfer has an apparent heterogeneous electron-transfer rate constant (k s ) of 5.9 ± 0.2 s -1 in case of the 5-layer electrode. The biosensor displays good electrocatalytic response to the reduction of H 2O 2, and the amperometric signal increase steadily with the concentration of H 2 O 2 in the range from 5 μM to 1.5 mM. The detection limit is 1 μM at pH 7.4. The apparent Michaelis-Menten constant (K m ) of the sensor is 0.53 mM. We assume that the observation of a direct electron transfer of cytochrome c on mesoporous carbon nanospheres may form the basis for a feasible approach for durable and reliable detection of H 2 O 2 . (author)

  1. The formation of scientists and technicians at the 'Centre d'Etudes Nucleaires' at Saclay; Formation des scientifiques et des techniciens au Centre d'Etudes Nucleaires de Saclay

    Energy Technology Data Exchange (ETDEWEB)

    Debiesse, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    The considerable needs in research workers and scientists which are asked by the nuclear energy obliged the Commissariat a l'Energie atomique to deal with a particular effort to increase the quantitative and qualitative formation of scientists. Most various ways have been used. 1- A National Institute of Nuclear Sciences and Nuclear Techniques was created, by a joint decree of the Prime Minister and the Minister for National Education (june 18, 1957). This Institute of Higher Teaching (250 students) indulges in the following matters: atomic engineering, quantum mechanics, theory and technic of particle accelerators, special metallurgy, radiobiology, thermic and mechanics of fluids. 2- An associated centre of the 'Conservatoire National des Arts et Metiers' waeated (200 students) for technical assistants, drawers, etc. 3- In contribution with both electronic industry and Ministry of Work, the Centre d'Etudes Nucleaires contributes to an accelerated formation of technical assistants into Professional Centres. Conclusion: Training of scientists and research workers is one of the most important activities of the Centre d'Etudes Nucleaires de Saclay. Without losing its technical efficiency, it has supplied and varied means adapted to the various purposes that we shall reach. (author)Fren. [French] Les besoins considerables actuels et previsibles en chercheurs et scientifiques necessites par l'avevement de l'energie nucleaire imposaient au Commissariat a I'Energie atomique un effort particulier pour augmenter la formation quantitative et qualitative des scientifiques. Les moyens les plus divers ont ete mis en oeuvre: 1- Creation de l'Institut National des Sciences et Techniques Nucleaires par decret de la Presidence du Conseil et de l'Education Nationale en date du 18.6.57. Cet Institut d'Enseignement Superieur (250 etudiants) donne des cours en: genie atomique, mecanique quantique, theorie et technique des Accelerateurs de particules, metallurgie speciale, radiobiologie

  2. Investigation of the glide modes of single crystals of beryllium; Etude des modes de glissement de monocristaux de beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Regnier, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1969-05-01

    The flow characteristics of single crystals of beryllium specially oriented for slip along a single plane and a single direction have been thoroughly investigated. The elastic limit and the strain hardening in basal glide have been investigated in the temperature range (-195 deg. C, 400 deg. C) in tension as well as in compression. Observation of the slip lines and of the dislocation configurations have also been made in addition to the mechanical tests. The prismatic slip has been studied in greater detail: tensile tests have been performed on specimens carefully oriented at different temperatures, strain rates and with varying orientations of the basal and of the prism planes. Tests have also been made in the micro-strain range; the slip lines and the dislocation arrangements were observed in detail. The very unusual variation of the elastic limit with temperature is not due to impurities but to a cross slip mechanism. A model of dislocation locking is proposed to account for the experimental results. This mechanism assumes that the a-bar dislocations may also dissociate on the prism planes [101-bar 0]. Various possible dissociations are suggested, the most probable of which corresponds to the phase transformation: Hexagonal close packed to body centered cubic. This proposal can be extended to account for the relative ease of glide on the different systems in the hexagonal close packed metals. (author) [French] L' ecoulement de monocristaux de berylliurn deformes en glissement basal et en glissement prismatique a ete etudie sur des echantillons orientes de maniere a favoriser au maximum la deformation suivant une seule direction d'un seul systeme de glissement. L'influence de la temperature sur la limite elastique et la consolidation en glissement basal a ete etudie depuis -195 deg. C jusqu' 400 deg. C sur des echantillons deformes en tension et sur d'autres deformes en compression. Ces essais mecaniques ont ete completes par l'observation des lignes de

  3. Covalent dimers of 1,3-diphenylisobenzofuran for singlet fission: synthesis and electrochemistry.

    Science.gov (United States)

    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.

  4. Chemically immobilised carbon nanotubes on silicon: Stable surfaces for aqueous electrochemistry

    International Nuclear Information System (INIS)

    Flavel, Benjamin S.; Garrett, David J.; Lehr, Joshua; Shapter, Joseph G.; Downard, Alison J.

    2010-01-01

    Diazonium ion chemistry has been used to electrochemically graft aminophenyl layers onto p-type silicon (1 0 0) substrates. A condensation reaction was used to immobilise single-walled carbon nanotubes with high carboxylic acid functionality directly to this layer. Electrochemical monitoring of the aminophenyl groups confirmed the formation of an amide linkage between the single-walled carbon nanotubes and the aminophenyl layer. The carbon nanotube electrode showed high stability and good electrochemical performance in aqueous solution. At moderate scan rates the Ru(NH 3 ) 6 +3/+2 couple exhibited quasi-reversible electron transfer kinetics with a standard heterogenous rate constant of 1.2 x 10 -3 cm s -1 at the covalently-linked carbon nanotube surface. The electrode thus combines the advantages of a silicon substrate for easy integration into sophisticated electrical and electronic devices, carbon nanotubes for desirable electrochemical properties, and stability in aqueous medium for future applications in environmental sensing.

  5. Development of a gas-ionization {beta}-spectrometer; Etude et realisation d'un spectrometre {beta} a ionisation gazeuse

    Energy Technology Data Exchange (ETDEWEB)

    Le Du, R [Commissariat a l' Energie Atomique, Bruyeres-le-Chatel (France). Centre d' Etudes

    1968-05-15

    We intend to develop in our laboratory a {beta}-spectrometer. This apparatus will have two main objectives: 1 - the determination of the nature and the degree of purity of certain {beta}-emitting radioactive substances; 2 - the study of an activity calibration process for {beta}-emitting radioactive sources. (author) [French] Nous nous proposons d'etudier et de realiser dans notre laboratoire un spectrometre {beta}. Cet appareil aura deux buts principaux: 1 - determiner la nature et le degre de purete de certains corps radioactifs emetteurs {beta}; 2 - permettre l'etude d'un procede d'etalonnage en activite de sources radioactives emetteurs {beta}. (auteur)

  6. Stable isotope separation; Separations physicochimiques d'isotopes stables realisations et etudes de petites productions

    Energy Technology Data Exchange (ETDEWEB)

    Botter, F; Molinari, Ph; Dirian, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-07-01

    Pure deuterium has been separated from gaseous mixtures of hydrogen and deuterium by band displacement chromatography, using columns of palladium on a support. The best results were obtained with columns of Pd on sintered {alpha} alumina. With a column of this type, of total capacity about 2 liters, a preparative apparatus of low dead volume has been built which produces 1 liter of pure D{sub 2} from a 50 p. 100 D{sub 2}, 50 p. 100 100 H{sub 2} mixture in about 12 minutes. As a first approximation chromatography is likened theoretically to counter current fractionation, neglecting superficial resistance to the exchange. and also longitudinal diffusions. The number of theoretical plates required necessary for a certain enrichment of the gas phase is determined graphically or by calculation, enabling comparisons to be made between the efficiencies of columns containing different amounts of palladium. Thermal Diffusion: For the separation of hydrogen isotopes a thermal diffusion installation, made of stainless steel and entirely tele-commanded has been constructed. The separation cascade is made up of two identical pairs of hot wire columns. Each pair can work separately or they may be connected by a thermosyphon. The temperature of the hot wire is kept at around 1000 deg C by direct current. With this installation, hydrogen samples with a deuterium content lower than o,5 ppm were obtained from a gas originally containing 32 ppm. It was thus possible to prepare tritium of 99,3 p. 100 concentration from gas with an initial content of 6 p. 100. For quantitative separation of xenon enriched five time in {sup 124}Xe by thermal diffusion, two identical cascades were constructed, each consisting of 5 columns, working in parallel and the two being connected by thermosyphon or by a capillary tube linked to a thermal gas oscillation. The central tungsten wire is heated to 1200 deg C. The columns are grouped like cluster of a heat exchanger, in shell of 30 cm diameter through

  7. Preparation and study of dialkyl nitroxide radicals; Preparation et etude de radicaux nitroxydes diacyles

    Energy Technology Data Exchange (ETDEWEB)

    Chenavas, P. [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    These radicals are obtained by oxidation of N-hydroxy-imides with lead tetracetate or p-nitro-perbenzoic acid. These imides are prepared by heating dicarboxylic acids anhydrides with benzyloxy-amine followed by catalytic hydrogenation of N-benzyloxy-imides so obtained. Two series of radicals have mainly been studied, the first concerning five-membered cyclic imides, the second six-membered cyclic imides, these molecules having methyls substituents or no on the carbon ring. N. M. R. spectra of some O-benzyl-imides have been analysed. These different results have made it possible to study the conformation and stereochemistry of these imides. (author) [French] Ces radicaux sont obtenus par oxydation d'imides N-hydroxyles par le tetracetate de plomb ou l'acide p-nitroperbenzoique; ces imides sont prepares par chauffage d'anhydrides de diacides en presence de benzyloxyamine suivie d'une hydrogenation catalytique des N-benzyloxyimides ainsi obtenus. Deux series de radicaux ont principalement ete etudies: la premiere relative a des imides cycliques a cinq chainons, la seconde a des imides cycliques a six chainons, ces molecules ayant des substituants methyles ou non sur la chaine carbonee. Les derives O-benzyles de quelques-uns de ces imides ont ete analyses en R. M. N. Ces differents resultats ont permis une etude de la conformation et de la stereochimie de ces imides. (auteur)

  8. The abject gaze and the homosexual body: Flandrin's Figure d'Etude.

    Science.gov (United States)

    Camille, M

    1994-01-01

    This article charts the history of the reception, reproduction and appropriation of a single image that has recently become a kind of "gay icon"--the Figure d'Etude in the Louvre, painted by Hippolyte Flandrin in 1835. Initially no more than a neo-classical academic exercise, the formal emptiness of this picture meant that it could be re-invested and reinscribed with new meanings and new titles at every turn. Emblematic of the anxious visibility/invisibility of the newly discovered homosexual body during a period when the gaze still had to be kept a dark secret, Flandrin's image only "came out" in its later photographic reworkings by Frederick Holland Day and Baron von Gloeden. After being reproduced for a specifically homosexual audience early this century, the popular Romantic pose of the young man curled-up in profile became a standard one, reappearing recently in the photographs of Robert Mapplethorpe. The inactive, abject and inward-turned isolation of the figure with its narcissistic self-absorption makes it, in my view, a profoundly negative stereotype of the gay gaze and the homosexual body. Flandrin's figure nonetheless appears today on gay merchandise world-wide as a sign of our separate and secluded subject positions and our community's unwillingness to radically alter older imposed and inherited classical stereotypes.

  9. Study of copper fluorination; Contribution a l'etude de la fluoruration du cuivre

    Energy Technology Data Exchange (ETDEWEB)

    Gillardeau, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-02-01

    This report deals with the action of fluorine on copper. Comprehensive descriptions are given of the particular technological methods and of the preparation of the reactants. This fluorination reaction has been studied at medium and low fluorine pressures. A nucleation and growth phenomenon is described. The influence of a pollution of the gas phase on the fluorination process is described. The solid-state reaction between cupric fluoride and cooper has also been studied. A special study has been made of the growth of copper deposits by thermal decomposition of gaseous fluorides. (author) [French] Ce rapport traite de la reaction du fluor sur le cuivre. Les methodes technologiques particulieres ainsi que les preparations des reactifs sont largement developpees. Cette reaction de fluoruration est etudiee sous pressions moyennes et sous basses pressions de fluor. Un phenomene de germination et croissance est decrit. L'influence de la pollution de la phase gazeuse sur le processus de fluoruration est rapportee. La reaction a l'etat solide du fluorure cuivrique sur le cuivre a egalement ete etudiee. La croissance de depots de cuivre par decomposition thermique des fluorures de cuivre gazeux fait l'objet d'une etude speciale. (auteur)

  10. Preparation and study of dialkyl nitroxide radicals; Preparation et etude de radicaux nitroxydes diacyles

    Energy Technology Data Exchange (ETDEWEB)

    Chenavas, P [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    These radicals are obtained by oxidation of N-hydroxy-imides with lead tetracetate or p-nitro-perbenzoic acid. These imides are prepared by heating dicarboxylic acids anhydrides with benzyloxy-amine followed by catalytic hydrogenation of N-benzyloxy-imides so obtained. Two series of radicals have mainly been studied, the first concerning five-membered cyclic imides, the second six-membered cyclic imides, these molecules having methyls substituents or no on the carbon ring. N. M. R. spectra of some O-benzyl-imides have been analysed. These different results have made it possible to study the conformation and stereochemistry of these imides. (author) [French] Ces radicaux sont obtenus par oxydation d'imides N-hydroxyles par le tetracetate de plomb ou l'acide p-nitroperbenzoique; ces imides sont prepares par chauffage d'anhydrides de diacides en presence de benzyloxyamine suivie d'une hydrogenation catalytique des N-benzyloxyimides ainsi obtenus. Deux series de radicaux ont principalement ete etudies: la premiere relative a des imides cycliques a cinq chainons, la seconde a des imides cycliques a six chainons, ces molecules ayant des substituants methyles ou non sur la chaine carbonee. Les derives O-benzyles de quelques-uns de ces imides ont ete analyses en R. M. N. Ces differents resultats ont permis une etude de la conformation et de la stereochimie de ces imides. (auteur)

  11. Study of {gamma}'s in Naiade; Etude des gamma de Naiade

    Energy Technology Data Exchange (ETDEWEB)

    Millot, J P; Rastoin, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    Following a study of the gamma sources, the flux of gamma of different energies in the swimming pool is investigated. The biological dose can thus be obtained by calculation, and compared with the results given by photographic plates. The influence of photoneutrons is estimated by calculation, and research is being carried out on their influence on the thermal neutron flux curve on the axis of the uranium plate, with the plate emitting neutrons and with the plate protected by boral. (author) [French] Apres l'etude des sources de gamma, l'on etudie le flux de gamma de differentes energies dans la piscine. La dose biologique peut etre obtenue ainsi par le calcul et comparee avec les resultats donnes par les plaques photographiques. L'influence des photoneutrons est estimee par le calcul et l'on recherche leur influence sur la courbe de flux de neutrons thermiques sur l'axe de la plaque d'uranium, la plaque emettant des neutrons et la plaque protegee par du boral. (auteur)

  12. Technological study of organic fluids; Etudes technologiques des fluides caloporteurs organique

    Energy Technology Data Exchange (ETDEWEB)

    Leveque, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-07-01

    Under contract to EURATOM (MM. VAN der VENNE and HANNAERT), the C.E.A. and the Progil Society have collaborated on a technological study of the terphenyls. The results obtained from the radiolysis and pyrolysis of the product OM2 (70 p. 100 m-terphenyl, 25 p. 100 o-terphenyl, 5 p. 100 p-terphenyl) are reported. Using two pile loops at temperatures up to 450 deg. C, a phenomena of accelerated pyrolysis on the radiolized material has been demonstrated. Some by-products of the petroleum industry have also been studied, with a view to finding substitutes for terphenyl. (author) [French] Le C.E.A. et la Societe PROGIL ont entrepris en commun sous contrat EURATOM (MM. VAN der VENNE et HANNAERT) une etude technologique des terphenyles. Les resultats de radiolyse et de pyrolyse obtenus sur le produit OM2 (70 p. 100 m-terphenyle, 25 p. 100 o-terphenyle. 5 p. 100 de p-terphenyle) sont exposes. L'exploitation de deux boucles en pile jusqu'a des temperatures de 450 deg. C a mis en evidence un phenomene de pyrolyse acceleree sur le produit radiolyse. On a etudie egalement quelques sous-produits de l'industrie petroliere dans le but de trouver des substituts au terphenyle. (auteur)

  13. Underground nuclear explosions. Geological survey of the cavities; Explosions nucleaires souterraines etude geologique des cavites

    Energy Technology Data Exchange (ETDEWEB)

    Faure, J [Commissariat a l' Energie Atomique, Bruyeres-le-Chatel (France). Centre d' Etudes

    1969-07-01

    A geological survey of underground nuclear explosions makes it possible to determine the main characteristics of the cavity formed. The lower portion is spherical; the same was very likely true of the roof, which collapses in the majority of media with the exception of rock-salt. Its radius, for a given bomb size, can vary by a factor of two according to the type of rock. The lay-out of its contents depends on the characteristics of the solid and liquid products at the moment of the roof collapse; according to the medium involved, mixing of the rubble and the mud-flow occurs (granite) or does not occur (tuff and alluvia). In all media, the average physical properties can be evaluated. (author) [French] L'etude geologique d'explosions nucleaires souterraines permet de determiner les principaux caracteres de la cavite creee. Sa partie inferieure est spherique; il en etait vraisemblablement de meme de sa voute, effondree dans la plupart des milieux a l'exception du sel gemme. Son rayon, a energie d'engin egale, varie selon les roches du simple au double. La disposition de son contenu depend des caracteristiques des produits solides et liquides au moment de la chute du toit; selon le cas, il n'y a pas (tuf et alluvions) ou il y a (granite) melange des eboulis et des laves. Dans tous les milieux, les proprietes physiques moyennes peuvent etre evaluees. (auteur)

  14. Contribution towards the study of {beta}{yields}{alpha} transformation in uranium and its alloys (1962); Contribution a l'etude de la transformation {beta}{yields}{alpha} dans l'uranium et ses alliages (1962)

    Energy Technology Data Exchange (ETDEWEB)

    Aubert, H. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1962-05-15

    The kinetics of the transformation of uranium alloys containing 0.5 - 0.75 - 1.0 - 1.5 and 3 atoms per cent have been studied. The influence of heat treatment before decomposition has been discussed. The study of the transformation characteristics such as kinetics, residual phases, phenomena connected with the coherence between phases, reversibility below the equilibrium temperature, shows the following mechanisms exhibited during the decomposition of the {beta} phase on lowering the temperature: 1 ) eutectoid, 2) bainitic, 3) martensitic. The study of the TTT diagrams of alloys containing decreasing percentages of chromium indicates that the unalloyed uranium transforms without maintaining the coherence above 600 deg. C, where as at lower temperatures the transformation is mainly martensitic. The various alloying elements can be characterised by their influence on the three TTT curves corresponding to the three possible transformation mechanisms. The ability of the uranium alloys to alpha grain refining during isothermal decomposition or ambient temperature quenching is directly connected with the characteristics of the TTT diagrams and especially to the mode of bainitic transformation. (author) [French] II a ete etudie la cinetique de transformation des alliages uranium-chrome de teneur 0,5 - 0,75 - 1 - 1,5 - et 3 atomes pour cent. L'influence des traitements thermiques precedant la decomposition a ete discutee. L'etude des caracteristiques de la transformation: cinetique, phases residuelles, phenomenes lies a la coherence entre phases, reversibilite au-dessous de la temperature d'equilibre, permet de conclure que la decomposition met en jeu successivement les trois mecanismes eutectoide, bainitique et martensitique quand la temperature baisse. L'etude de l'evolution des diagrammes TTT quand la teneur en Cr decroit indique que dans l'uranium non allie la transformation se fait sans maintien de la coherence au-dessus de 600 deg. C; a

  15. Contribution towards the study of {beta}{yields}{alpha} transformation in uranium and its alloys (1962); Contribution a l'etude de la transformation {beta}{yields}{alpha} dans l'uranium et ses alliages (1962)

    Energy Technology Data Exchange (ETDEWEB)

    Aubert, H [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1962-05-15

    The kinetics of the transformation of uranium alloys containing 0.5 - 0.75 - 1.0 - 1.5 and 3 atoms per cent have been studied. The influence of heat treatment before decomposition has been discussed. The study of the transformation characteristics such as kinetics, residual phases, phenomena connected with the coherence between phases, reversibility below the equilibrium temperature, shows the following mechanisms exhibited during the decomposition of the {beta} phase on lowering the temperature: 1 ) eutectoid, 2) bainitic, 3) martensitic. The study of the TTT diagrams of alloys containing decreasing percentages of chromium indicates that the unalloyed uranium transforms without maintaining the coherence above 600 deg. C, where as at lower temperatures the transformation is mainly martensitic. The various alloying elements can be characterised by their influence on the three TTT curves corresponding to the three possible transformation mechanisms. The ability of the uranium alloys to alpha grain refining during isothermal decomposition or ambient temperature quenching is directly connected with the characteristics of the TTT diagrams and especially to the mode of bainitic transformation. (author) [French] II a ete etudie la cinetique de transformation des alliages uranium-chrome de teneur 0,5 - 0,75 - 1 - 1,5 - et 3 atomes pour cent. L'influence des traitements thermiques precedant la decomposition a ete discutee. L'etude des caracteristiques de la transformation: cinetique, phases residuelles, phenomenes lies a la coherence entre phases, reversibilite au-dessous de la temperature d'equilibre, permet de conclure que la decomposition met en jeu successivement les trois mecanismes eutectoide, bainitique et martensitique quand la temperature baisse. L'etude de l'evolution des diagrammes TTT quand la teneur en Cr decroit indique que dans l'uranium non allie la transformation se fait sans maintien de la coherence au-dessus de 600 deg. C; a plus basse temperature la

  16. Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

    Science.gov (United States)

    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.

  17. E. P. R. spectroscopic study of nitroxide mono- and bi-radicals; Etude par spectroscopie de resonance paramagnetique electronique de monoradicaux et de biradicaux nitroxydes

    Energy Technology Data Exchange (ETDEWEB)

    Lemaire, H [Commissariat a l' Energie Atomique, Grenoble, 38 (France). Centre d' Etudes Nucleaires

    1967-07-01

    A nitroxide is a molecule containing the group N-O where the oxygen atom made only one bond instead of the usual two. The main advantage of these radicals is their exceptional stability; this allows the study of well defined chemical structures while varying at will the experimental conditions. Studies by electron paramagnetic resonance of nitroxide mono-radicals have given the principal directions and the principal values of the electron-nitrogen nucleus hyperfine tensor and of the anisotropic g-factor tensor. The results were then related to the electronic structure of radicals. An understanding was obtained of the influence of the solvent on the principal values of the tensors, and the marked differences observed in the broadening of hyperfine lines when the medium become viscous. In the nitroxide biradicals, the hyperfine spectra depends not only on the magnetic interactions relative to each monomer, but also on the magnitude of the exchange interaction between the singlet and the triplet states of the dimer; the biradicals studied here are the first organic compounds which show clearly the influence of this exchange on the hyperfine structure. The two unpaired electrons also interact by a magnetic dipolar interaction: in the intermediate case, this can be used to derive the sign of the exchange interaction if the bi-radical is studied in a liquid crystal. Just as for mono-radicals, the hyperfine spectra of bi-radicals show selective broadening in viscous media, which is caused by an overall motional modulation of the anisotropic tensors. This gives another way to determine the sign of the exchange interaction. (author) [French] On appelle nitroxyde une molecule contenant le groupement N-O ou l'atome d'oxygene n'a satisfait qu'une seule liaison de valence sur les deux qui lui sont habituelles. L'interet majeur de ces radicaux reside dans leur exceptionnelle stabilite, permettant ainsi de faire varier a loisir les conditions experimentales d'etude de produits

  18. Chemically immobilised carbon nanotubes on silicon: Stable surfaces for aqueous electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Flavel, Benjamin S., E-mail: ben.flavel@flinders.edu.a [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand); School of Chemistry, Physics and Earth Sciences, Flinders University, Sturt Road, Bedford Park, Adelaide, South Australia 5001 (Australia); Garrett, David J.; Lehr, Joshua [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology, Private Bag 4800, Christchurch 8140 (New Zealand); Shapter, Joseph G. [School of Chemistry, Physics and Earth Sciences, Flinders University, Sturt Road, Bedford Park, Adelaide, South Australia 5001 (Australia); Downard, Alison J., E-mail: alison.downard@canterbury.ac.n [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology, Private Bag 4800, Christchurch 8140 (New Zealand)

    2010-04-30

    Diazonium ion chemistry has been used to electrochemically graft aminophenyl layers onto p-type silicon (1 0 0) substrates. A condensation reaction was used to immobilise single-walled carbon nanotubes with high carboxylic acid functionality directly to this layer. Electrochemical monitoring of the aminophenyl groups confirmed the formation of an amide linkage between the single-walled carbon nanotubes and the aminophenyl layer. The carbon nanotube electrode showed high stability and good electrochemical performance in aqueous solution. At moderate scan rates the Ru(NH{sub 3}){sub 6}{sup +3/+2} couple exhibited quasi-reversible electron transfer kinetics with a standard heterogenous rate constant of 1.2 x 10{sup -3} cm s{sup -1} at the covalently-linked carbon nanotube surface. The electrode thus combines the advantages of a silicon substrate for easy integration into sophisticated electrical and electronic devices, carbon nanotubes for desirable electrochemical properties, and stability in aqueous medium for future applications in environmental sensing.

  19. Photophysics and electrochemistry relevant to photocatalytic water splitting involved at solid–electrolyte interfaces

    KAUST Repository

    Shinagawa, Tatsuya

    2016-08-04

    Direct photon to chemical energy conversion using semiconductor-electrocatalyst-electrolyte interfaces has been extensively investigated for more than a half century. Many studies have focused on screening materials for efficient photocatalysis. Photocatalytic efficiency has been improved during this period but is not sufficient for industrial commercialization. Detailed elucidation on the photocatalytic water splitting process leads to consecutive six reaction steps with the fundamental parameters involved: The photocatalysis is initiated involving photophysics derived from various semiconductor properties (1: photon absorption, 2: exciton separation). The generated charge carriers need to be transferred to surfaces effectively utilizing the interfaces (3: carrier diffusion, 4: carrier transport). Consequently, electrocatalysis finishes the process by producing products on the surface (5: catalytic efficiency, 6: mass transfer of reactants and products). Successful photocatalytic water splitting requires the enhancement of efficiency at each stage. Most critically, a fundamental understanding of the interfacial phenomena is highly desired for establishing "photocatalysis by design" concepts, where the kinetic bottleneck within a process is identified by further improving the specific properties of photocatalytic materials as opposed to blind material screening. Theoretical modeling using the identified quantitative parameters can effectively predict the theoretically attainable photon-conversion yields. This article provides an overview of the state-of-the-art theoretical understanding of interfacial problems mainly developed in our laboratory. Photocatalytic water splitting (especially hydrogen evolution on metal surfaces) was selected as a topic, and the photophysical and electrochemical processes that occur at semiconductor-metal, semiconductor-electrolyte and metal-electrolyte interfaces are discussed.

  20. How to Develop Electrochemistry SETS-Based Interactive E-Book?

    Science.gov (United States)

    Munawwarah, M.; Anwar, S.; Sunarya, Y.

    2017-09-01

    This study aims to develop SETS-based interactive e-book teaching material through 4S TMD methode. The research methode in this study is the Development Research (RD) Richey and Klein that consists of design, phase, and evaluation. The design step was to analyze and plan the types of teaching materials instructional developed. There are 12 indicators from 3 standard competences that produced in selection step based new curriculum, the compatibility subject matter and indicators, and the relations between value and subject matter. Structuring steps yield concept map, macro structure, and multiple representation that were arranged to be first draft of teaching material that was used for develop the instruments for characterization step. Chatacterization test have been done to students in 12nd grades with 68 texts. Characterization results indicated that there were some texts included to difficult text. Difficult texts have been reduced with the ways back to qualitative steps and particulation. The second draft of teaching material was arranged based the results of didactic reduction of difficult texts. This draft was used for arranged interactive e-book. The characteristics of this SETS-based interactive e-book that developed were mention about the connection between science with environment, technology, and society. This interactive e-book consists of animation, task, and quizes that taken the interaction of students directly.

  1. Effect of Concentration on the Electrochemistry and Speciation of the Magnesium Aluminum Chloride Complex Electrolyte Solution.

    Science.gov (United States)

    See, Kimberly A; Liu, Yao-Min; Ha, Yeyoung; Barile, Christopher J; Gewirth, Andrew A

    2017-10-18

    Magnesium batteries offer an opportunity to use naturally abundant Mg and achieve large volumetric capacities reaching over four times that of conventional Li-based intercalation anodes. High volumetric capacity is enabled by the use of a Mg metal anode in which charge is stored via electrodeposition and stripping processes, however, electrolytes that support efficient Mg electrodeposition and stripping are few and are often prepared from highly reactive compounds. One interesting electrolyte solution that supports Mg deposition and stripping without the use of highly reactive reagents is the magnesium aluminum chloride complex (MACC) electrolyte. The MACC exhibits high Coulombic efficiencies and low deposition overpotentials following an electrolytic conditioning protocol that stabilizes species necessary for such behavior. Here, we discuss the effect of the MgCl 2 and AlCl 3 concentrations on the deposition overpotential, current density, and the conditioning process. Higher concentrations of MACC exhibit enhanced Mg electrodeposition current density and much faster conditioning. An increase in the salt concentrations causes a shift in the complex equilibria involving both cations. The conditioning process is strongly dependent on the concentration suggesting that the electrolyte is activated through a change in speciation of electrolyte complexes and is not simply due to the annihilation of electrolyte impurities. Additionally, the presence of the [Mg 2 (μ-Cl) 3 ·6THF] + in the electrolyte solution is again confirmed through careful analysis of experimental Raman spectra coupled with simulation and direct observation of the complex in sonic spray ionization mass spectrometry. Importantly, we suggest that the ∼210 cm -1 mode commonly observed in the Raman spectra of many Mg electrolytes is indicative of the C 3v symmetric [Mg 2 (μ-Cl) 3 ·6THF] + . The 210 cm -1 mode is present in many electrolytes containing MgCl 2 , so its assignment is of broad interest

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

    Science.gov (United States)

    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.

  3. Synthesis, structure and electrochemistry of cationic diruthenium complexes of the type [(N-N)2Ru2(CO)2(.mu.-OOCFc)]+ containing a ferrocenecarboxylato bridge and two chelating aromatic diimine ligands

    Czech Academy of Sciences Publication Activity Database

    Auzias, M.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

    2007-01-01

    Roč. 692, č. 4 (2007), s. 755-760 ISSN 0022-328X Institutional research plan: CEZ:AV0Z40400503 Keywords : carbonyl ligands * carboxylato ligands * ferrocenyl substituents * diimine ligands Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

  4. Erratum to Electrochemical single-molecule conductivity of duplex and quadruplex DNA [Current Opinion in Electrochemistry volume 7 (2018) 66-74 of duplicate article](S2451910317300984)(10.1016/j.coelec.2017.09.005)

    DEFF Research Database (Denmark)

    Zhang, Ling; Zhang, Jingdong; Ulstrup, Jens

    2018-01-01

    The Publisher regrets that this article is an accidental duplication of an article that has already been published in Current Opinion in Electrochemistry Volume 4 Issue 1 (2017) 166-174, http://dx.doi.org/10.1016/j.coelec.2017.11.009. The duplicate article has therefore been withdrawn. The full...

  5. Influence of ionic liquids on the direct electrochemistry of glucose oxidase entrapped in nanogold-N,N-dimethylformamide-ionic liquid composite film

    International Nuclear Information System (INIS)

    Li, Jiangwen; Fan, Cong; Xiao, Fei; Yan, Rui; Fan, Shuangshuang; Zhao, Faqiong; Zeng, Baizhao

    2007-01-01

    Glucose oxidase (GOD) immobilized in nanogold particles (NAs)-N,N-dimethylformamide (DMF) composite film on glassy carbon (GC) electrode exhibits a pair of quasi-reversible and unstable peaks due to the redox of flavin adenine dinucleotide (FAD) of GOD. When ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF 4 ) or trihexyltetradecylphosphorium bis (trifluoromethylsulfony) (P 666,14 NTf 2 ) is introduced in the film, the peaks become small. But ILs 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF 6 ) and 1-octyl-3-methylimidazolium hexafluorophate (OMIMPF 6 ) make the peaks large and stable. In different composite films the formal potential (E 0 ') of GOD is different. UV-vis spectra show that the GOD dispersed in these films almost retains its native structure and there are weak interactions between ILs and GOD. Electrochemical impedance spectra display that NAs can promote the electron transfer between FAD and GC electrode; and ILs can affect the electron transfer through interacting with GOD. The thermal stability of GOD entrapped in NAs-DMF-ILs composite films is also influenced by ILs, and it follows such order as: in NAs-DMF-OMIMPF 6 > in NAs-DMF-BMIMPF 6 ∼ in NAs-DMF-BMIMBF 4 > in NAs-DMF. In addition, GOD immobilized in NAs-DMF-OMIMPF 6 and NAs-DMF-BMIMPF 6 films shows good catalytic activity to the oxidation of glucose. The I max of H 2 O 2 and the apparent K m (Michaelis-Menten constant) for the enzymatic reaction are calculated

  6. A gold electrode modified with hemoglobin and the chitosan Fe3O4 nanocomposite particles for direct electrochemistry of hydrogen peroxide

    International Nuclear Information System (INIS)

    Wang, Yuan-Hong; Yu, Chun-Mei; Pan, Zhong-Qin; Wang, Yu-Fei; Guo, Jian-Wei; Gu, Hai-Ying

    2013-01-01

    We report on a novel electrochemical biosensor that was fabricated by immobilizing hemoglobin (Hb) onto the surface of a gold electrode modified with a chitosan Fe 3 O 4 nano-composite. The Fe 3 O 4 nanoparticles were prepared by co-precipitation and have an average size of 25 nm. They were dispersed in chitosan solution to obtain the chitosan Fe 3 O 4 nano-composite particles with an average diameter of 35 nm as verified by transmission electron microscopy. X-ray diffraction patterns and Fourier transform IR spectroscopy confirmed that the crystallite structure of the Fe 3 O 4 particles in the nano-composite has remained unchanged. At pH 7.0, Hb gives a pair of redox peaks with a potential of about −0.21 V and −0.36 V. The Hb on the film maintained its biological activity and displays good electrocatalytic reduction activity towards hydrogen peroxide. The linear range for the determination of H 2 O 2 is from 2.3 μM to 9.6 mM, with a detection limit at 1.1 μM concentration (at S/N = 3). The apparent Michaelis-Menten constant is 3.7 mM and indicates the high affinity of Hb for H 2 O 2 . This biosensor also exhibits good reproducibility and long-term stability. Thus, it is expected to possess potential applications in the development of the third-generation electrochemical biosensors (author)

  7. Direct electrochemistry of myoglobin in a layer-by-layer film on an ionic liquid modified electrode containing CeO2 nanoparticles and hyaluronic acid

    International Nuclear Information System (INIS)

    Gao, R.; Zheng, J.; Zheng, X.

    2011-01-01

    We describe an ionic liquid modified electrode (CPE-IL) for sensing hydrogen peroxide (HP) that was modified by the layer-by-layer technique with myoglobin (Mb). In addition, the surface of the electrode was modified with CeO 2 nanoparticles (nano-CeO 2 ) and hyaluronic acid. UV-vis and FTIR spectroscopy confirmed that Mb retains its native structure in the composite film. Scanning electron microscopy showed that the nano-CeO 2 closely interact with Mb to form an inhomogeneously distributed film. Cyclic voltammetry reveals a pair of quasi-reversible redox peaks of Mb, with the cathodic peak at -0. 357 V and the anodic peak at -0. 269 V. The peak separation (ΔE p ) and the formal potential (E σ ) are 88 mV and -0. 313 V (vs. Ag/AgCl), respectively. The Mb immobilized in the modified electrode displays an excellent electrocatalytic activity towards HP in the 0. 6 to 78. 0 μM concentration range. The limit of detection is 50 nM (S/N = 3), and then the Michaelis-Menten constant is 71. 8 μM. We believe that such a composite film has potential to further investigate other redox proteins and in the fabrication of third-generation biosensors. (author)

  8. Study: control of atomic energy power plant; Etude de la regulation d'une installation atomique productrice d'energie

    Energy Technology Data Exchange (ETDEWEB)

    Dautray, R; Leny, J C [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    We are studying the control of a very flexible atomic power plant, able to supply an independent network. Two systems have been examined: in the first the moderator pre-heats the light water, in the second, this preheating is dispensed with, subsequent to a study of the dynamics of the plant. Very complete linear approximation study is being effected on the model of the second system, all effects being taken into account. The reactor is stable at all power levels, though slight reactivity or load variations cause undamped power oscillations around the equilibrium level. (author)Fren. [French] Nous etudions la regulation d'une installation atomique d'une grande souplesse, pouvant eventuellement fournir de l'energie a un reseau isole. Deux versions de l'installation sont etudiees: dans la premiere le moderateur sert a rechauffer l'eau industrielle, mais l'etude dynamique conduit a supprimer ce rechauffage, ce qui donne la deuxieme version. On effectue sur celle-ci une etude en approximation lineaire tres complete ou l'on tient compte de differents effets. L'installation se montre stable a tous les niveaux de puissance. Toutefois, de petites perturbations de reactivite ou de charge entrainent des oscillations de puissance mal amorties autour de la position d'equilibre. (auteur)

  9. Methods for studying the radioactive contamination of plants (1963); Methodes d'etude de la contamination radioactive des vegetaux (1963)

    Energy Technology Data Exchange (ETDEWEB)

    Coulon, R; Jeanmaire, L; Michon, G [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1963-07-01

    The authors first define the doctrine which led to the devising of a method for studying the radioactive pollution of plants, based on the use of simple techniques, having the possibility of being adapted for routine work, and so devised that each stage is proceeded with only if the preceding one justifies it. For each stage a study is effected comparing the results obtained by the use of more exact techniques. The second part describes in detail the techniques used. (authors) [French] Dans une premiere partie lea auteurs definissent la doctrine qui leur a permis d'elaborer une methode d'etude de la pollution radioactive des vegetaux, basee sur l'utilisation de techniques simples, se pretant au travail de serie et concues de telle maniere que chaque etape n'est abordee que si la precedente le justifie. Chaque etape fait l'objet d'une etude qui compare les resultats a ceux obtenue par des techniques plus precises. La deuxieme partie decrit dans le detail les techniques utilisees. (auteurs)

  10. Direct Democracy

    DEFF Research Database (Denmark)

    Beramendi, Virginia; Ellis, Andrew; Kaufman, Bruno

    While many books on direct democracy have a regional or national approach, or simply focus on one of the many mechanisms associated with direct democracy, this Handbook delves into a global comparison of direct democracy mechanisms, including referendums, citizens' initiatives, agenda initiatives...... learned. In addition, the uniquely comprehensive world survey outlines direct democracy provisions in 214 countries and territories and indicates which, if any, of these provisions are used by each country or territory at both the national and sub-national levels. Furthermore, the world survey includes...

  11. Directing 101.

    Science.gov (United States)

    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…

  12. Contribution to the study of french pitchblendes; Contribution a l'etude des pechblendes francaises

    Energy Technology Data Exchange (ETDEWEB)

    Geffroy, J. [Commissariat a l' Energie Atomique, Lab. de Mineralogie, Centre de Chatillon (France). Centre d' Etudes Nucleaires; Sarcia, J.A. [Commissariat a l' Energie Atomique, Div. de la Crouzille, Haute Vienne (France). Centre d' Etudes Nucleaires

    1955-07-01

    The authors first review the characteristics of uraninite-pitchblende, as deduced of present literature. They set apart from typical pitchblende a black oxide aspect, which probably corresponds to neo-formations, and a 'para-pitchblende' aspect, which they relate to deep sur-oxidation of normal pitchblende. They insist on the easy replacement of pitchblende by silica. and give indications as to changes in vein stones (fluorite, quartz, etc...). A detailed study of paragenesis and successions in french uranium districts follows (including discussion of uranium of uranium-bearing coals). The authors attempt to classify french pitchblende veins. They are chiefly epithermal and poor in satellite ores. Three types of deposits are identified: massive - pitchblende type, silica type, fluorite type. These deposits, as those of Portugal, are included in granite, Central-European peri-batholitic types where uranium associates which Ni, Co, Bi and Ag, are in France both rare and poor. Finally, the authors attempt to bring out in the european Hercynian area a particular distribution of paragenetic types. (authors) [French] Les auteurs recapitulent d'abord les caracteres et les occurences de l'uraninite - pechblende, tels qu'ils peuvent etre degages de l'actuelle bibliographie. Ils exposent ensuite les faits qui du point de vue mineralogique seulement ressortent de l'etude mineralogique et chalcographique des pechblendes francaises et de leurs satellites. Ils distinguent de la pechblende-type un facies oxyde noir; correspondant probablement a une neoformation, et un facies parapechblende, qui est rapporte a une sur oxydation hypogene de la pechblende proprement dite. Ils insistent sur le facile remaniement de la pechblende par la slice; et donnent quelques precisions sur les modifications des gangues (fluorine, quartz, etc...). Suit l'etude detaillee des parageneses et des successions dans les districts uraniferes francais: Divisions du

  13. The dynamic behaviour of heat exchangers; Etude du comportement dynamique des echangeurs de chaleur

    Energy Technology Data Exchange (ETDEWEB)

    Fonteray, J; Rozenholc, M [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1963-07-01

    In order to study the dynamics of nuclear power plants, one needs mathematical models made up of ordinary differential equations. This report deals with models for heat exchangers. These models allow exact evaluations of the temperatures for any steady state. The deformation of the temperature maps during transients is taken into account. To do this, average temperatures are evaluated keeping In mind, on one hand the partial differential equations, on the other hand, the physical phenomenons which are involved. Seven ordinary differential equations at most, are necessary for one heat exchanger. Theses models were compared with mathematically exact ones and also with experimental results, that EDF was able to measure on EDF-1 heat exchangers. The results appear to be correct. (authors) [French] Les etudes de dynamique sur les centrales nucleaires exigent l'elaboration de modeles apparaissant sous forme d'equations differentlelles ordinaires. Ce rapport est consacre a la recherche de modeles d'echangeurs. Dans ces modeles les temperatures sont calculees exactement pour n'importe quel regime permanent. Pour tenir compte de la deformation des distributions de temperature en regime transitoire, on evalue les temperatures moyennes dans l'echangeur en s'appuyant, d'une part, sur les equations aux derivees partielles et, d'autre part, sur une analyse des phenomenes physiques. Les modeles contiennent au plus sept equations differentielles ordinaires. Ces modeles ont ete compares aux modeles mathematiques exacts et aussi a des resultats experimentaux, obtenus par l'EDF, sur les echangeurs d'EDF-1. Les resultats paraissent satisfaisants. (auteurs)

  14. Etude theorique et experimentale des evaporateurs de dioxyde de carbone operant dans des conditions de givrage

    Science.gov (United States)

    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

  15. Pegase: safety studies - experimental study of burn-out risks in transient operation; Pegase: etude de surete - etude experimentale des risques de burn out en regime transitoire

    Energy Technology Data Exchange (ETDEWEB)

    Vernier, P [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1968-07-01

    canal chaud se met en etat de calefaction au bout de 0.1 s et que sa temperature atteint 500 C en 0.8 s. Les regimes hydrodynamiques rencontres dans les canaux apres l'accident sont des regimes d'expulsion periodiques de periodes courtes 0.2 a 0.5 s, caracteristiques de l'ebullition a basse pression. L'etude en regime permanent de la redistribution de debit dans un by-pass a donne des flux PHI{sub R} de redistribution de 190 W/cm{sup 2} pour une vitesse de 4.5 m/s a 50 C et de 175 W/cm{sup 2} a 60 C. Ces valeurs sont a majorer de 25 pour cent pour une vitesse de 6 m/s. On a montre la distinction a faire entre flux critique PHI{sub C} en regime periodique d'expulsion et flux de redistribution PHI{sub R} en regime permanent. (auteur)

  16. Directing Creativity

    DEFF Research Database (Denmark)

    Darsø, Lotte; Ibbotson, Piers

    2008-01-01

    In this article we argue that leaders facing complex challenges can learn from the arts, specifically that leaders can learn by examining how theatre directors direct creativity through creative constraints. We suggest that perceiving creativity as a boundary phenomenon is helpful for directing it....... Like leaders, who are caught in paradoxical situations where they have to manage production and logistics simultaneously with making space for creativity and innovation, theatre directors need to find the delicate balance between on one hand renewal of perceptions, acting and interaction...... and on the other hand getting ready for the opening night. We conclude that the art of directing creativity is linked to developing competencies of conscious presence, attention and vigilance, whereas the craft of directing creativity concerns communication, framing and choice....

  17. Study of the dynamic behaviour of the reactor Rapsodie; Etude du comportement dynamique de la pile rapsodie

    Energy Technology Data Exchange (ETDEWEB)

    Abdon, R; Chaigne, M [Commissariat a l' Energie Atomique, Cadarache (France). Centre d' Etudes Nucleaires

    1964-07-01

    . The investigation of the control, carried out on analog computer, served to determine the different possible means of starting and changing the conditions of the reactor as well as its automatic control. The calculations were examined in the totality by the construction of a training simulator composed of a board similar to the control board of the reactor, all of whose commands (reactivity and flows) work on an analogue computer which resolves in the real time the dynamic equations of the reactor and which reproduces simultaneously all the parameters representing the state of the installation (power, period, temperatures, etc. ) in the case of various incidents as well as under normal conditions of functioning. (authors) [French] On sait que le developpement des reacteurs surgenerateurs a neutrons rapides pose des problemes nouveaux d'une part dans les domaines mecanique et thermique et d'autre part en ce qui concerne leur comportement dynamique et leur surete. La pile RAPSODIE a ete l'objet de tres nombreuses etudes dynamiques effectuees sur machines analogiques et digitales, pour deux versions du combustible (metal et oxyde). Apres elaboration des modeles mathematiques representatifs de l'ensemble de l'installation (bloc pile et circuit de refroidissement) tant du point de vue neutronique que du point de vue thermodynamique, on a mis au point les schemas analogiques et les codes digitaux utilisables pour mener a bien les simulations d'incidents, de conduite et de stabilite du reacteur. On s'est attache, par rapport aux methodes habituelles a obtenir une precision plus grande, par un decoupage en zones plus fines, par l'emploi de formulations plus representatives du systeme reel, voire solubles analytiquement. Les etudes d'incidents ont ete effectuees par voie analogique pour l'ensemble de l'installation et par voie digitale pour l'etude du bloc pile seul ou de l'installation fonctionnant avec un seul circuit thermique. Un programme complementaire special - qui, a

  18. Depth probing of the hydride formation process in thin Pd films by combined electrochemistry and fiber optics-based in situ UV/vis spectroscopy.

    Science.gov (United States)

    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.

  19. End-of-Discharge and End-of-Life Prediction in Lithium-Ion Batteries with Electrochemistry-Based Aging Models

    Science.gov (United States)

    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.

  20. Electrochemistry in near-critical and supercritical fluids. 3. Studies of Br/sup -/, I/sup -/, and hydroquinone in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Flarsheim, W.J.; Tsou, Y.M.; Trachtenberg, I.; Johnston, K.P.; Bard, A.J.

    1986-07-31

    A new type of apparatus has been constructed for carrying out electrochemistry in near-critical and supercritical aqueous solutions. The following systems have been studied at a platinum electrode: H/sub 2/O/O/sub 2/, I/sup -//I/sub 2/, Br/sup -//Br/sub 2/, and hydroquinone/benzoquinone. The compact alumina flow cell can be heated or cooled quickly and can be recharged with fresh electrolyte solution while at high temperature and pressure. A large reduction in the potential required for the electrolysis of water was observed. Diffusivities have been measured for iodide ions and hydroquinone. General agreement with the Stokes-Einstein model was observed in the temperature range 25-375/sup 0/C.