Sample records for direct electrochemistry etude

  1. Study of hydrogenases activity inhibition by O{sub 2} and direct electrochemistry; Etude de l'inhibition par O{sub 2} de l'activite d'hydrogenases par electrochimie directe

    Energy Technology Data Exchange (ETDEWEB)

    Baffert, C.; Leger, Ch.; Leroux, F.; Bertrand, P.; Guigliarelli, B. [Laboratoire de Bioenergetique et d' Ingenierie des proteines, BIP-CNRS, 13 - Marseille (France)


    At the present time, a great effort of research is made on the identification and the design of enzymes insensitive or low sensitive to O{sub 2}. In parallel, it seems important to understand the inhibition mechanisms in order to propose mutations able to limit this inhibition. The Protein Film Voltametry allows to obtain data which can not be observed or quantitatively obtained by other techniques. The enzyme is immobilized directly on the electrode and the electronic transfer is direct. The redox state of the enzyme depends on the potential of the electrode and the catalytic current is proportional to the enzyme activity. The data obtained for the Ni-Fe hydrogenase (Desulfovibrio fructosovorans) and for the Fe hydrogenase (Clostridium Acetobutylicum) will be compared to the data obtained for hydrogenases of other organisms, by Protein Film Voltametry as well as by other techniques. (O.M.)

  2. 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 ...

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

    Directory of Open Access Journals (Sweden)

    Periasamy Arun Prakash


    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.

  4. Direct Electrochemistry of Horseradish Peroxidase-Gold Nanoparticles Conjugate

    Directory of Open Access Journals (Sweden)

    Chanchal K. Mitra


    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

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

    International Nuclear Information System (INIS)

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


    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 H 2 O 2 , 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. - Graphical abstract: The utilization of N-doped graphene enables direct electrochemistry of hemoglobin with a pair of well-defined redox peaks appearing. - Highlights: • Nitrogen-doped graphene (NG) was synthesized by a solvothermal method. • NG was used for the investigation on direct electrochemistry of hemoglobin with carbon ionic liquid electrode. • The Hb modified electrode exhibited excellent electrocatalytic activity toward different substrates

  6. Direct Electrochemistry of Methanobactin Functionalized Gold Nanoparticles on Au Electrode. (United States)

    Xin, Jiaying; Dou, Boxin; Wang, Zhenxing; Wang, Yan; Xia, Chungu; Liu, Zhongfan


    Mathanobatins (Mb, Mbtins) were immobilized successfully on nanometer-sized gold colloid particles associated with β-mercaptoethylamine. The structures of Mb functionalized gold nanoparticles were characterized and confirmed by UV-vis spectroscopy (UV-vis), FTIR spectra and electrochemical analyses. Direct electron transfer between Mb or copper-loading Mbtins and the modified electrode was investigated without the aid of any electron mediator. The copper-loading Mbtins act as a better electrocatalyst for the reduction of H2O2 than Mb. The copper-loading Mb, with which gold nanoparticles were functionalized, as a model enzyme, was immobilized on gold electrode to construct a novel H2O2 biosensor. In pH 6.4 phosphate buffer solution, the reduction and oxidation peak potentials of Mb functionalized gold nanoparticles modified Au electrode (copper-loading Mbtins) were 0.115 and 0.222 V. On the surface, capacitance per unite area (Cd) of Mb functionalized gold nanoparticles modified electrode were 38 μF cm-2. The immobilized Mb displayed the features of a peroxidase and gave an excellent electrocatalytic response to the reduction of H2O2. The detection limit of Mb functionalized gold nanoparticles (copper-loading) were 09 × 10-5 mA/M (S/N = 3). The Michaelis-Menten constant (Km) was 0.787 mM. Good stability and sensitivity were assessed for the biosensor.

  7. 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


    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

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

    Directory of Open Access Journals (Sweden)

    Lijun Yan


    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.

  9. 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: [Institute of Analytical Chemistry for Life Science, School of Public Health, Nantong University, Nantong 226007 (China)


    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.

  10. Layered double hydroxides functionalized with anionic surfactant: Direct electrochemistry and electrocatalysis of hemoglobin

    International Nuclear Information System (INIS)

    Li Maoguo; Chen Shuihong; Ni Fang; Wang Yinling; Wang Lun


    Direct electrochemistry of hemoglobin (Hb), which was immobilized on the glass carbon electrode (GCE) modified with Zn-Al layered double hydroxide (LDH) functionalized with sodium dodecylsulfonate (SDS), was investigated. The resulting electrode (Hb/LDH-SDS/GCE) gave a well-defined redox couple for HbFe(III)/Fe(II) with a formal potential of about -0.34 V (vs. AgCl/Ag) in pH 7.0 buffer. The electron-transfer rate constant was estimated to be 2.6 s -1 . The Hb/LDH-SDS/GCE exhibited a remarkable electrocatalytic activity for the reduction of hydrogen peroxide (H 2 O 2 ). The low calculated apparent Michaelis-Menten constant (K M app ) was 456 μM. Based on the high catalytic activity of Hb immobilized on LDH-SDS modified electrode to the reduction of H 2 O 2 , LDH functionalized with SDS is expected to have widely potential applications for development of new biosensors and biocatalysis

  11. 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


    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.

  12. 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.


    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

  13. 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: [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)


    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.

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

    Palanisamy, Selvakumar; Karuppiah, Chelladurai; Chen, Shen-Ming


    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. Direct electrochemistry and electrocatalysis of horseradish peroxidase with hyaluronic acid-ionic liquid-cadmium sulfide nanorod composite material

    Energy Technology Data Exchange (ETDEWEB)

    Zhu Zhihong [Institute of Nano-Science and Technology Center, Huazhong Normal University, Wuhan 430079 (China); Li Xia; Wang Yan [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Zeng Yan [Institute of Nano-Science and Technology Center, Huazhong Normal University, Wuhan 430079 (China); Sun Wei, E-mail: [College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Huang Xintang [Institute of Nano-Science and Technology Center, Huazhong Normal University, Wuhan 430079 (China)


    A new composite material consisted of hyaluronic acid (HA), ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF{sub 4}) and cadmium sulfide (CdS) nanorod was fabricated and used for the immobilization of horseradish peroxidase (HRP) on the surface of a carbon ionic liquid electrode (CILE), which was prepared with 1-ethyl-3-methyl-imidazolium ethylsulphate ([EMIM]EtOSO{sub 3}) as modifier. Spectroscopic results indicated that HRP remained its native structure in the composite film. Based on the synergistic effect of the materials used, an obvious promotion to the direct electron transfer efficient between HRP and CILE was achieved with a pair of well-defined redox peaks appeared in 0.1 mol L{sup -1} phosphate buffer solution, indicating the realization of the direct electrochemistry of HRP. The immobilized HRP showed good electrocatalytic activity towards the reduction of trichloroacetic acid and H{sub 2}O{sub 2} with the electrochemical parameters calculated. Based on the fabricated electrode, a new third-generation electrochemical biosensor was constructed with good stability and reproducibility.

  16. Analytical and physical electrochemistry

    CERN Document Server

    Girault, Hubert H


    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

  17. 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


    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...

  18. 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


    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)

  19. Horseradish peroxidase immobilized in TiO2 nanoparticle films on pyrolytic graphite electrodes: direct electrochemistry and bioelectrocatalysis

    International Nuclear Information System (INIS)

    Zhang Yan; He Pingli; Hu Naifei


    Horseradish peroxidase (HRP)-TiO 2 film electrodes were fabricated by casting the mixture of HRP solution and aqueous titania nanoparticle dispersion onto pyrolytic graphite (PG) electrodes and letting the solvent evaporate. The HRP incorporated in TiO 2 films exhibited a pair of well-defined and quasi-reversible cyclic voltammetric peaks at about -0.35 V versus saturated calomel electrode (SCE) in pH 7.0 buffers, characteristic of HRP-Fe(III)/Fe(II) redox couple. The electron exchange between the enzyme and PG electrodes was greatly enhanced in the TiO 2 nanoparticle film microenvironment. The electrochemical parameters such as apparent heterogeneous electron transfer rate constant (k s ) and formal potential (E deg. ') were estimated by fitting the data of square wave voltammetry with nonlinear regression analysis. The HRP-TiO 2 film electrodes were quite stable and amenable to long-time voltammetric experiments. The UV-Vis spectroscopy showed that the position and shape of Soret absorption band of HRP in TiO 2 films kept nearly unchanged and were different from those of hemin or hemin-TiO 2 films, suggesting that HRP retains its native-like tertiary structure in TiO 2 films. The electrocatalytic activity of HRP embedded in TiO 2 films toward O 2 and H 2 O 2 was studied. Possible mechanism of catalytic reduction of H 2 O 2 with HRP-TiO 2 films was discussed. The HRP-TiO 2 films may have a potential perspective in fabricating the third-generation biosensors based on direct electrochemistry of enzymes

  20. Fullerene-nitrogen doped carbon nanotubes for the direct electrochemistry of hemoglobin and its application in biosensing. (United States)

    Sheng, Qinglin; Liu, Ruixiao; Zheng, Jianbin


    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.

  1. Direct electrochemistry and electrocatalysis of hemoglobin protein entrapped in graphene and chitosan composite film. (United States)

    Xu, Huifeng; Dai, Hong; Chen, Guonan


    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.

  2. 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


    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.

  3. 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:


    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.

  4. Direct electrochemistry and electrochemical catalysis of immobilized hemoglobin in an ethanol-water mixture. (United States)

    Liu, Hui-Hong; Wan, Yong-Qing; Zou, Guo-Lin


    Hemoglobin (Hb) was immobilized on a glassy carbon electrode (GCE) surface by konjac glucomannan (KGM). KGM hydrogel films on GCE have relatively high stabilities in aqueous-ethanol mixtures. The entrapped hemoglobin undergoes fast direct electron transfer reactions in aqueous-organic solvent mixtures. The peak current is bigger, the peak-to-peak separation smaller and the formal potential observed in the cyclic voltammogram is more negative for Hb-KGM/GCE in ethanol-PBS compared to Hb-KGM/GCE in PBS. The electrochemical properties of the Hb in aqueous-organic solution are almost unchanged from with those observed for the purely aqueous solution, suggesting that water pools in the KGM hydrogel play an important role in preventing changes in conformation and making proteins unreactive with polar organic solvents. The immobilized Hb was able to catalyze the reduction of nitric oxide, peroxides (hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2-butanone peroxide), and the dehalogenation of haloethanes (hexachloroethane, pentachloroethane, tetrachloroethane, etc.). The stability and reproducibility of the modified electrode meant that it could be used to determine these substances.

  5. 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


    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.

  6. 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


    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.

  7. Modern aspects of electrochemistry

    CERN Document Server

    Vayenas, Constantinos G


    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.

  8. Silicon: electrochemistry and luminescence

    NARCIS (Netherlands)

    Kooij, Ernst Stefan


    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

  9. 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


    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.

  10. Fabrication of biomembrane-like films on carbon electrodes using alkanethiol and diazonium salt and their application for direct electrochemistry of myoglobin. (United States)

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


    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.

  11. Instrumental methods in electrochemistry

    CERN Document Server

    Pletcher, D; Peat, R


    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. 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: [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: [College of Sciences, Nanjing Tech University, Nanjing 211816 (China)


    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

  13. 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


    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

  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: [Institute of Analytical Chemistry for Life Science, School of Public Health, Nantong University, Nantong 226019 (China)


    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. Modern Aspects of Electrochemistry 40

    CERN Document Server

    White, Ralph E


    This volume in the acclaimed series Modern Aspects of Electrochemistry starts with a dedication to the late Professor Brian Conway who for 50 years helped to guide this series to its current prominence. The remainder of the volume is then devoted to the following topics: PEM fuel cells; the use of graphs in electrochemical reaction newtworks; nanomaterials in Lithium-ion batteries; direct methanolf fuel cells (two chapters); fuel cell catalyst layers. The book is for electrochemists, electrochemical engineers, fuel cell workers and energy generation workers.

  16. 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: [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


    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.

  17. An electrochemical aptasensor for thrombin detection based on direct electrochemistry of glucose oxidase using a functionalized graphene hybrid for amplification. (United States)

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


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

  18. Nanostructured materials in electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Eftekhari, Ali (ed.) [Avicenna Institute of Technology, Cleveland, OH (United States)


    Providing the unique and vital link between the worlds of electrochemistry and nanomaterials, this reference and handbook covers advances in electrochemistry through the nanoscale control of electrode structures, as well as advances in nanotechnology through electrochemical synthesis strategies. It demonstrates how electrochemical methods are of great scientific and commercial interest due to their low cost and high efficiency, and includes the synthesis of nanowires, nanoparticles, nanoporous and layered nanomaterials of various compositions, as well as their applications - ranging from superior electrode materials to energy storage, biosensors, and electroanalytical devices. (orig.)

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

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


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

  20. Self-assembly of glucose oxidase on reduced graphene oxide-magnetic nanoparticles nanocomposite-based direct electrochemistry for reagentless glucose biosensor. (United States)

    Pakapongpan, Saithip; Poo-Arporn, Rungtiva P


    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

  1. 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


    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

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

    Chekin, Fereshteh; Gorton, Lo; Tapsobea, Issa


    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.

  3. Theoretical Chemistry and Electrochemistry

    Indian Academy of Sciences (India)


    solvation dynamics and molecular dynamics. In electrochemistry, the papers discuss a variety of topics like electrochemical nanostructures, photoelectrochemistry, electron transfer, capacitors, etc. We hope that this issue of Journal of Chemical Sciences will be a fitting tribute to the scientific genius of SKR. We wish to thank ...

  4. 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...

  5. Electrochemistry on nanopillared electrodes

    Directory of Open Access Journals (Sweden)

    Chandni Lotwala


    Full Text Available The addition of nanopillars to electrodes increases their electrochemical capabilities through an increase in electroactive surface area. The nanopillars can be applied on either cathodes or anodes to engage in reduction-oxidation reactions. This minireview summaries some work on cyclic voltammetry, chronoamperometry, impedance change on nanopillared surface and compared their electrochemistry behavior on planar surfaces.

  6. 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


    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

  7. 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: [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)


    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.

  8. Direct electrochemistry of redox proteins

    NARCIS (Netherlands)

    Heering, H.A.


    The goal of the project was to obtain more detailed insight in interactions between redox proteins and solid electrodes and the mechanisms of electron transfer. In addition to this, the influence of the protein environment on the redox properties of the active site and the possible

  9. Electrochemistry of nucleic acids

    Czech Academy of Sciences Publication Activity Database

    Paleček, Emil; Bartošík, Martin


    Roč. 112, č. 6 (2012), s. 3427-3481 ISSN 0009-2665 R&D Projects: GA ČR(CZ) GAP301/11/2055; GA MŠk(CZ) ME09038; GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : nucleic acids electrochemistry * DNA biosensors * DNA damage Subject RIV: BO - Biophysics Impact factor: 41.298, year: 2012

  10. Applications of electrochemistry in medicine

    CERN Document Server

    Schlesinger, Mordechay


    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.

  11. Folds and Etudes (United States)

    Bean, Robert


    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…

  12. Solved problems in electrochemistry

    International Nuclear Information System (INIS)

    Piron, D.L.


    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

  13. Electrochemistry "Discovery" Course for Undergraduates (United States)

    May, Michael Alan; Gupta, Vijay K.


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

  14. Electrochemistry of organic, bioactive compounds and biopolymers

    Czech Academy of Sciences Publication Activity Database

    Fojta, Miroslav; Navrátil, Tomáš


    Roč. 146, č. 5 (2015), s. 721-721 ISSN 0026-9247 Institutional support: RVO:68081707 ; RVO:61388955 Keywords : electrochemistry * biopolymers Subject RIV: CG - Electrochemistry Impact factor: 1.131, year: 2015

  15. Electrochemistry and dye-sensitized solar cells

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav


    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)

  16. 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


    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

  17. Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs. (United States)

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


    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.

  18. Direct electrochemistry of hemoglobin immobilized on the water-soluble phosphonate functionalized multi-walled carbon nanotubes and its application to nitric oxide biosensing. (United States)

    Li, Pan; Ding, Yu; Lu, Zhaoyang; Li, Ying; Zhu, Xiaoshu; Zhou, Yiming; Tang, Yawen; Chen, Yu; Cai, Chenxin; Lu, Tianhong


    The direct electron transfer and electrocatalysis of hemoglobin (Hb) immobilized on the phosphonate functionalized multi-walled carbon nanotubes (MWCNTs) are investigated. Fourier transform infrared (FT-IR) spectra, UV-vis spectra and cyclic voltammetry (CV) analyses reveal that the phosphonate functionalized MWCNTs have good biocompatibility for Hb immobilization, and promote the electron communication between Hb and electrode. The immobilized Hb shows a pair of redox peak with a formal potential of -406 ± 10 mV (vs. SCE) and the electrochemical behavior of Hb was a surface-controlled process in a pH 7.0 phosphate buffer solution. And the immobilized Hb can act in an electrocatalytic manner in the electrochemical reduction of nitric oxide (NO). Accordingly, an unmediated NO electrochemical biosensor is constructed. Under optimized experimental conditions, the NO electrochemical biosensor shows the fast response (less than 3s), the wide linear range (1.5 × 10(-7) to 2.7 × 10(-4)M) and the low detection limit (1.5 × 10(-8)M), which is attributed to the good mass transport, the large Hb loading per unit area and the fast electron transfer rate of Hb. © 2013 Elsevier B.V. All rights reserved.

  19. Modified fractal iron oxide magnetic nanostructure: A novel and high performance platform for redox protein immobilization, direct electrochemistry and bioelectrocatalysis application. (United States)

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


    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.

  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


    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. Etude des interactions entre les differents acteurs des interventions ...

    African Journals Online (AJOL)

    Etude des interactions entre les differents acteurs des interventions sous directives communautaires et changements obtenus au Benin et au Togo. P.V. Malou Adom, Ch. P. Makoutode, T Gnaro, A.R. Ouro-Koura, E.M. Ouendo, G Napo-Koura, M Makoutode ...

  2. 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.


    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)

  3. Medicinal electrochemistry: integration of electrochemistry, medicinal chemistry and computational chemistry. (United States)

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


    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.


    Indian Academy of Sciences (India)

    DR. Rama Kant

    much remains to be done because roughness is absolutely ubiquitous and often is the major obstacle to an understanding and control of reality.” -Mandelbrot. Wolff (1926): ... Durham University, U.K. local surface shape. Singh & Kant, Proc. Roy.

  5. 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


    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.)

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

    International Nuclear Information System (INIS)


    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

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

    International Nuclear Information System (INIS)


    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

  8. Composite Solid Electrodes - Tool for Organic Electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Navrátil, Tomáš


    Roč. 15, č. 17 (2011), s. 2996-3013 ISSN 1385-2728 R&D Projects: GA AV ČR IAA400400806; GA ČR GAP206/11/1638 Institutional research plan: CEZ:AV0Z40400503 Keywords : amperometry * composite solid electrodes * polarography Subject RIV: CG - Electrochemistry Impact factor: 3.064, year: 2011

  9. Electrochemistry and Radioactive Wastes: A Scientific Overview

    Directory of Open Access Journals (Sweden)

    Maher Abed Elaziz


    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.

  10. 2015 CEC Annual Workshop on Electrochemistry (United States)


    Electrochemical Biosensors . 2:05-2:55 Minshu Du and Allen Bard, The University of Texas at Austin Mechano-electrochemistry and Strain Effects. 2:55-3:15 electrochemical biosensor technology, modern electrochemical glucose assays are currently used by about 150 million people to monitor and manage... Biosensors ” Dr. Rebecca Lai is currently the Susan J. Rosowski Associate Professor of Chemistry at the University of Nebraska-Lincoln. Dr. Lai

  11. Imaging mass spectrometry tackles interfacial challenges in electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xiao-Ying


    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.

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

    National Research Council Canada - National Science Library

    Santos, Elizabeth; Schmickler, Wolfgang


    "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...

  13. Electrochemistry of titanium dioxide: some aspects and highlights

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav


    Roč. 12, č. 1 (2012), s. 131-142 ISSN 1527-8999 R&D Projects: GA MŠk LC510; GA AV ČR KAN200100801; GA AV ČR IAA400400804 Institutional research plan: CEZ:AV0Z40400503 Keywords : titanium dioxide * electrochemistry * photoelectrochemistry Subject RIV: CG - Electrochemistry Impact factor: 4.377, year: 2012

  14. Development of an Electrochemistry Teaching Sequence Using a Phenomenographic Approach (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…

  15. Carbon Nanotube Electrodes for Hot-Wire Electrochemistry

    Czech Academy of Sciences Publication Activity Database

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


    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

  16. Application and Utilization of Electrochemistry in Organic Chemistry

    Czech Academy of Sciences Publication Activity Database

    Navrátil, Tomáš


    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

  17. The electrochemistry of IGSCC mitigation

    International Nuclear Information System (INIS)

    Macdonald, D.D.


    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.)

  18. Applications of ultrasound in electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Silva Martinez, Susana


    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

  19. Electrochemistry-based Battery Modeling for Prognostics (United States)

    Daigle, Matthew J.; Kulkarni, Chetan Shrikant


    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.

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

    International Nuclear Information System (INIS)


    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

  1. 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. (United States)

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


    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.

  2. 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.


    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

  3. 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:; Guo, Kai; Duan, Congyue; Chen, Xianjin; Zhu, Zhenfeng


    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}.

  4. 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.


    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

  5. 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.


    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.

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

    Indian Academy of Sciences (India)


    College of Chemistry and Molecular Engineering,. Key Laboratory, Eco-Chemical Engineering of Ministry of Education,. Qingdao University of Science and Technology, Qingdao 266042, P.R. ..... Due to the presence of ILs in the carbon paste, CILE had showed some advantages such as biocompatible interface and high ...

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

    Indian Academy of Sciences (India)


    to the deep burying of the electroactive prosthetic groups, the partly adsorptive denaturation of the pro- teins on the electrode surface or the unfavourable orientations at the electrodes, the heterogeneous electron transfer process of biomacromolecules is rather slower at the traditional electrode surface. Efforts were devoted ...

  8. Electrochemistry of plutonium in molten halides

    International Nuclear Information System (INIS)

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


    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. 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.


    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

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

    Czech Academy of Sciences Publication Activity Database

    Mueller, J. E.; Krtil, Petr; Kubler, L. A.; Jacob, T.


    Roč. 16, č. 29 (2014), s. 15029-15042 ISSN 1463-9076 Institutional support: RVO:61388955 Keywords : Bimetallic alloys * electrochemistry * catalysis Subject RIV: CG - Electrochemistry Impact factor: 4.493, year: 2014

  11. 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


    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.

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

    DEFF Research Database (Denmark)

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


    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...

  13. ETUDE - European Trade Union Distance Education. (United States)

    Creanor, Linda; Walker, Steve


    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. Chelating ionic liquids for reversible zinc electrochemistry. (United States)

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


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

  15. Developments in electrochemistry science inspired by Martin Fleischmann

    CERN Document Server

    Pletcher, Derek; Williams, David


    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

  16. 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


    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

  17. Using a Teaching Model To Correct Known Misconceptions in Electrochemistry. (United States)

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


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

  18. Facilitating Conceptual Change in Students' Understanding of Electrochemistry. (United States)

    Niaz, Mansoor


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

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

    Energy Technology Data Exchange (ETDEWEB)

    Liu, S.H.


    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.

  20. Introduction to Electrochemistry and the Use of Electrochemistry to Synthesize and Evaluate Catalysts for Water Oxidation and Reduction (United States)

    Hendel, Samuel J.; Young, Elizabeth R.


    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…

  1. Creating Pedagogical Etudes for Interactive Instruments


    Butler, Jennifer


    In this paper I discuss the importance of and need forpedagogical materials to support the development of newinterfaces and new instruments for electronic music. I describemy method for creating a graduated series of pedagogicaletudes composed using Max/MSP. The etudes will helpperformers and instrument designers learn the most commonlyused basic skills necessary to perform with interactiveelectronic music instruments. My intention is that the finalseries will guide a beginner from these init...

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


    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.

  3. Advances in molten salt electrochemistry towards future energy systems

    International Nuclear Information System (INIS)

    Ito, Yasuhiko


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

    CERN Document Server

    Fuchigami, Toshio; Inagi, Shinsuke


    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...

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


    Branch, Jack; Alibouri, Mehrdad; Cook, David A.; Richardson, Peter; Bartlett, Philip N.; Matefi-Tempfli, Maria; Matefi-Tempfli, Stefan; Bampton, Mark; Cookson, Tamsin; Connell, Phil; Smith, David


    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. These two innovations widen what can be achieved with supercritical fluid electrodeposition. The suitability of the reactor for electroanalytical experiments is demonstrated by studies of the voltammet...


    Energy Technology Data Exchange (ETDEWEB)



    Ruthenium is a metal of a considerable importance in electrochemical science and technology. It is a catalyst or co-catalyst material in Pt-Ru alloys for methanol- and reformate hydrogen-oxidation in fuel cells, while ruthenium oxide, a component in chlorine-evolution catalysts, represents an attractive material for electrochemical supercapacitors. Its facile surface oxidation generates an oxygen-containing species that provides active oxygen in some reactions. Ru sites in Pt-Ru catalysts increase the ''CO tolerance'' of Pt in the catalytic oxidation-reaction in direct methanol fuel cells (DMFC) and in reformate hydrogen-oxidation in proton exchange membrane fuel cells (PEMFC). The mechanism of Ru action is not completely understood, although current consensus revolves around the so-called ''bifunctional mechanism'' wherein Ru provides oxygenated species to oxidize CO that blocks Pt sites, and has an electronic effect on Pt-CO interaction. While various studies of polycrystalline Ru go back several decades those involving single crystal surfaces and the structural sensitivity of reactions on Ru surfaces emerged only recently. Using well-ordered single crystalline surfaces brings useful information as the processes on realistic catalysts are far too complex to allow identification of the microscopic reaction steps. In this article, we focus on progress in model systems and conditions, such as electrochemistry and electrocatalysis on bare and Pt-modified well-ordered Ru(0001) and Ru(10{bar 1}0) single-crystal surfaces. We also review current understanding of the mechanistic principles of Pt-Ru systems and a new development of a Pt submonolayer on Ru support electrocatalyst. Ruthenium crystallizes in a hexagonal close-packed structure, (hcp). Figure 1.1 shows the two single crystal surfaces of Ru. The Ru(0001) surface possesses the densest, i.e. hexagonal arrangement of atoms, Fig. 1.1a. The other plane, Ru(10{bar 1}0), can have

  7. 2010 Gordon Research Conference, Electrochemistry, January 9-15, 2010

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  8. Redox-capacitor to connect electrochemistry to redox-biology. (United States)

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


    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.

  9. Etude des comportements rheologiques des melanges de farine ble ...

    African Journals Online (AJOL)

    Etude des comportements rheologiques des melanges de farine ble/sorgho sans tanins issue de trois nouvelles varietes cultivees au Senegal et mise au point de pains a base de farines composees (ble/sorgho)

  10. Instrumental performance of an etude after three methods of practice. (United States)

    Vanden Ark, S


    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.

  11. 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


    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'...

  12. The 59th annual meeting of the International Society of Electrochemistry in Seville. (United States)

    Baltruschat, Helmut


    Electrochemistry down to the molecular level was the main theme of the 59th annual meeting of the International Society of Electrochemistry (ISE, see logo). Around 1400 scientists from all over the world met in Seville to discuss modern aspects, progress in methods and new mechanistic insights.

  13. 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


    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

  14. 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.


    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 including...

  15. Microbial Electrochemistry and its Application to Energy and Environmental Issues (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

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

    Directory of Open Access Journals (Sweden)

    Sanju Gupta


    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. Plastic reactor suitable for high pressure and supercritical fluid electrochemistry

    DEFF Research Database (Denmark)

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


    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....... These two innovations widen what can be achieved with supercritical fluid electrodeposition. The suitability of the reactor for electroanalytical experiments is demonstrated by studies of the voltammetry of decamethylferrocene in supercritical difluromethane and for electrodeposition is demonstrated...

  18. Etude des risques de défaillances d'un réseau de télécommunications soumis aux effets directs ou indirects de la foudre


    Ribeiro, José


    Direct or indirect effects of lightning may engender important damage on telecommunication network. This thesis discusses how theoretical study of the coupling mechanism of lightning can be achieved especially when the strike point is located near or on a structure composed of a telecommunication pylon. specifically, we outline a topological approach using software base on the transmission line theory (TLT) which allows us to characterise the surges induced on a telecommunication cable for di...

  19. Cobalt-cadmium bimetallic porphyrin coordination polymers for electrochemistry application (United States)

    Wang, C. Y.; Cui, G. Y.; Ding, D.; Zhou, B.


    In this paper, we used tetra (4-carboxyphenyl) porphyrin (H2TCPP) and metal cadmium, cobalt as reactants to synthesize metal porphyrin coordination polymers that they had different metal ratio. They were expressed as Co1Cd3TCPP, Co1Cd1TCPP, Co3Cd1TCPP, respectively. The results were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and inductively coupled plasma atomic emission spectrometer (ICP). Herein, a series of metal porphyrin coordination polymers has multiple metal active centers and constructs electrochemistry sensors. In order to increase the conductivity, multi-walled carbon nanotubes (MWCNTs) can be used to modify the electrodes. The polymer/MWCNTs/GCE electrode was studied by cyclic voltammetry and chronoamperometry as sensor for sodium nitrite. The performance of Co1Cd1TCPP/MWCNTs/GCE electrode is best, the sensitivity for sodium nitrite is 350.95 mA M-1 cm-2 and the. The results indicate that metal porphyrin coordination polymers have excellent performance. It also enriches the application of metal porphyrin coordination polymer in electrochemistry sensor.

  20. Electroanalytical Evaluation of Nanoparticles by Nano-impact Electrochemistry (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. Electro-Fermentation - Merging Electrochemistry with Fermentation in Industrial Applications. (United States)

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


    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.

  2. Encyclopedia of electrochemistry. Vol. 4. Corrosion and oxide films

    Energy Technology Data Exchange (ETDEWEB)

    Stratmann, M. [Max-Planck-Institut fuer Eisenforschung GmbH, Duesseldorf (Germany); Frankel, G.S. (eds.) [Ohio State Univ., Columbus, OH (United States). Dept. of Materials Science and Engineering


    This book is one of the eleven volumes of the ''Encyclopaedia of Electrochemistry'' and provides both an introduction to the different fields of corrosion as well as a detailed overview of the subjects. The volume is divided into seven main chapters each of them containing some special papers written by well known specialists. The main chapters are structured as follows: 1. Fundamentals (of corrosion, thermodynamics, kinetics and transport phenomena in electrolytic corrosion); 2. Homogeneous corrosion of metallic materials in electrolytes; 3. Corrosion of oxide covered materials (Atmospheric corrosion; Passivity of metals, alloys, and semiconductors); 4. Localised corrosion phenomena (Crevice corrosion; Pitting corrosion; Intergranular corrosion); 5. Corrosion protection 6. Corrosion in special environments (Molten salt-induced corrosion of metals; High-temperature corrosion of metals by gases; Microbiologically influenced corrosion); and 7. Electrochemical techniques for corrosion.

  3. Ionic liquids in electrochemical devices and processes: managing interfacial electrochemistry. (United States)

    MacFarlane, Douglas R; Forsyth, Maria; Howlett, Patrick C; Pringle, Jennifer M; Sun, Jiazeng; Annat, Gary; Neil, Wayne; Izgorodina, Ekaterina I


    Many ionic liquids offer a range of properties that make them attractive to the field of electrochemistry; indeed it was electrochemical research and applications that ushered in the modern era of interest in ionic liquids. In parallel with this, a variety of electrochemical devices including solar cells, high energy density batteries, fuel cells, and supercapacitors have become of intense interest as part of various proposed solutions to improve sustainability of energy supply in our societies. Much of our work over the last ten years has been motivated by such applications. Here we summarize the role of ionic liquids in these devices and the insights that the research provides for the broader field of interest of these fascinating liquids.

  4. 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


    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)

  5. Bacterial biofilms investigated by atomic force microscopy and electrochemistry

    DEFF Research Database (Denmark)

    Hu, Yifan

    thesis, Atomic Force Microscopy (AFM) and electrochemistry have been applied to investigate three pathogenic medically important bacterial biofilms, i.e. Pseudomonas aeruginosa (cystic fibrosis pneumonia), Staphylococcus epidermidis (contamination of surgical catheters and indwelling equipment......) and Streptococcus mutans (dental caries). AFM was used to investigate the adhesion force on single live cell surfaces. Four different strains of Staphylococcus epidermidis in liquid aqueous environments were adressed. These strains were selected because of their special surface proteins related with the initial...... pattern of Streptococcus mutans biofilms. Five redox probes were chosen for cyclic voltammetry, i.e. positively, [Ru(NH3)6]3+/2+, [Co(phen)3]3+/2+ and [Co(terpy)2]3+/2+ (phen = 1,10-phenanthroline; terpy = 2,2’,2”-terpyridine) and negatively charged, [Fe(CN)6]3-/4-. [IrCl6]3-/4-. The inhibition...

  6. Proceedings of the twelfth ISEAC discussion meet on electrochemistry and its applications

    International Nuclear Information System (INIS)

    Aggarwal, Suresh K.


    This meet discusses recent advances in the applications of electrochemistry and allied topics like fuel cells, super-capacitors, lithium batteries, bio-sensors, hydrogen production, electroanalytical chemistry, ionic liquids, etc. Papers relevant to INIS are indexed separately

  7. 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

  8. Catalysis in electrochemistry from fundamental aspects to strategies for fuel cell development

    CERN Document Server

    Santos, Elizabeth


    Catalysis in Electrochemistry: From Fundamental Aspects to Strategies for Fuel Cell Development is a modern, comprehensive reference work on catalysis in electrochemistry, including principles, methods, strategies, and applications. It points out differences between catalysis at gas/surfaces and electrochemical interfaces, along with the future possibilities and impact of electrochemical science on energy problems. This book contributes both to fundamental science; experience in the design, preparation, and characterization of electrocatalytic materials; and the industrial application o

  9. 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


    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

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

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav


    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

  11. Direction des Etudes et Recherches Annual report 1980

    International Nuclear Information System (INIS)


    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

  12. Individuals achieve more accurate results with meters that are codeless and employ dynamic electrochemistry. (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    Asri MK


    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

  14. 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


    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)

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

    KAUST Repository

    Lee, W. Y.


    © 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.


    Directory of Open Access Journals (Sweden)

    Wiwik Widodo


    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%.

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

    Dopper, Sofia M.; Sjoer, Ellen


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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  19. 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


    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

  20. 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


    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

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

    Directory of Open Access Journals (Sweden)

    Ulrich Stimming


    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.

  2. Electrochemistry of Prebiotic Early Earth Hydrothermal Chimney Systems (United States)

    Hermis, N.; Barge, L. M.; Chin, K. B.; LeBlanc, G.; Cameron, R.


    Hydrothermal chimneys are self-organizing chemical garden precipitates generated from geochemical disequilibria within sea-vent environments, and have been proposed as a possible setting for the emergence of life because they contain mineral catalysts and transect ambient pH / Eh / chemical gradients [1]. We simulated the growth of hydrothermal chimneys in early Earth vent systems by using different hydrothermal simulants such as sodium sulfide (optionally doped with organic molecules) which were injected into an early Earth ocean simulant containing dissolved ferrous iron, nickel, and bicarbonate [2]. Chimneys on the early Earth would have constituted flow-through reactors, likely containing Fe/Ni-sulfide catalysts that could have driven proto-metabolic electrochemical reactions. The electrochemical activity of the chimney system was characterized non-invasively by placing electrodes at different locations across the chimney wall and in the ocean to analyze the bulk properties of surface charge potential in the chimney / ocean / hydrothermal fluid system. We performed in-situ characterization of the chimney using electrochemical impedance spectroscopy (EIS) which allowed us to observe the changes in physio-chemical behavior of the system through electrical spectra of capacitance and impedance over a wide range of frequencies during the metal sulfide chimney growth. The electrochemical properties of hydrothermal chimneys in natural systems persist due to the disequilibria maintained between the ocean and hydrothermal fluid. When the injection in our experiment (analogous to fluid flow in a vent) stopped, we observed a corresponding decline in open circuit voltage across the chimney wall, though the impedance of the precipitate remained lor. Further work is needed to characterize the electrochemistry of simulated chimney systems by controlling response factors such as electrode geometry and environmental conditions, in order to simulate electrochemical reactions

  3. 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 ...

  4. 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)


    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.

  5. In Situ Electrochemistry of Rechargeable Battery Materials: Status Report and Perspectives. (United States)

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


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

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

    Czech Academy of Sciences Publication Activity Database

    Klíma, Jiří


    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

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

    DEFF Research Database (Denmark)

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


    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...

  8. 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


    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

  9. Lithium insertion into TiO2 (anatase): electrochemistry, Raman spectroscopy, and isotope labeling

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav


    Roč. 18, č. 8 (2014), s. 2297-2306 ISSN 1432-8488 R&D Projects: GA ČR GA13-07724S Grant - others:COST(XE) CM1104 Institutional support: RVO:61388955 Keywords : TITANIUM-DIOXIDE ANATASE * LI-INSERTION * NANOCRYSTALLINE TiO2 Subject RIV: CG - Electrochemistry Impact factor: 2.446, year: 2014

  10. 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.


    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

  11. Computer-Animated Instruction and Students' Conceptual Change in Electrochemistry: Preliminary Qualitative Analysis (United States)

    Talib, Othman; Matthews, Robert; Secombe, Margaret


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

  12. Effect of Cooperative Learning Strategies on Students' Understanding of Concepts in Electrochemistry (United States)

    Acar, Burcin; Tarhan, Leman


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

  13. A Historical Analysis of the Daniell Cell and Electrochemistry Teaching in French and Tunisian Textbooks (United States)

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


    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.

  14. 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

  15. 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.


    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.

  16. Impact du deversement direct des eaux usees et de drainage dans ...

    African Journals Online (AJOL)

    directement sans aucun traitement prealable. L'objectif de cette etude est de determiner !'extension du ... is high and the use of the groundwater is not advised for irrigation. Keywords: Unconfined aquifer- Rising water level ...... [2] Bilgehan Nas & Ali Berktay, 2010. Groundwater quality mapping in urban groundwater using ...

  17. 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.


    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

  18. Direct evaluation of thyroid [sup 127]I and iodine overload: in vivo study by X-ray fluorescence and in vitro by SIMS microscopy. Evaluation directe de l'[sup 127]I thyroidien en situation de surcharge iodee: etude in vivo par fluorescence X et in vitro par microscopie ionique analytique

    Energy Technology Data Exchange (ETDEWEB)

    Briancon, C.; Jeusset, J.; Halpern, S.; Fragu, P. (Centre de Lutte Contre le Cancer Gustave-Roussy, 94 - Villejuif (France))


    This review describes the two methods which allow direct estimation of stable iodine ([sup 127] I) within thyroid gland either in vivo by X-ray fluorescence or in vitro by secondary ion mass spectrometry (SIMS) microscopy on tissue section. Although the measurement of thyroid iodine content (TIC) by X-ray fluorescence has little relevance for routine explorations of thyroid function, this is a valuable method for understanding complex pathophysiological conditions such as the thyroid adaptation to iodine overload. On the other hand, SIMS microscopy which is able to characterize the functional activity of thyroid tissue by measuring [sup 127] I concentration within the thyroid follicles, can be used to determine the extent to which exogeneous iodine affects the regulation of iodine within the thyroid follicles. Both methods were used to evaluate the quantitative changes in thyroid [sup 127] I induced by amiodarone iodine overload. TIC measurements shows that hyperthyroidism occured only in patients who increased their iodine stores, while the patients who developed hypothyroidism has low iodine stores. The SIMS microscopy data obtained in mice demonstrated that the thyroid response to amiodarone is related to dietary iodine intake leading to an increase in local iodine concentration in iodine deficient mice and to a decrease in iodine supplemented mice. This response is specific and different from that induced by an iodine overload. These results could explain that hyperthyroidism with high thyroid iodine content occured in areas with low thyroid iodine content in areas with a supplemented iodine diet.

  19. 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.


    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)

  20. 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.


    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)

  1. 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


    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

  2. 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


    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

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

    International Nuclear Information System (INIS)


    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 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

  4. 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


    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.

  5. Direct electrochemistry and electrocatalysis of lobetyolin via magnetic functionalized reduced graphene oxide film fabricated electrochemical sensor. (United States)

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


    A novel lobetyolin electrochemical sensor based on a magnetic functionalized reduced graphene oxide/Nafion nanohybrid film has been introduced in this work. The magnetic functionalized reduced graphene oxide was characterized by fourier transform infrared spectroscopy, atomic force microscope, X-ray diffraction, transmission electron microscopy and thermogravimetric analysis. The scanning electron microscopy characterized the morphology and microstructure of the prepared sensors, and the electrochemical effective surface areas of the prepared sensors were also calculated by chronocoulometry method. The electrochemical behavior of lobetyolin on the magnetic functionalized reduced graphene oxide/Nafion nanohybrid modified glassy carbon electrode was investigated by cyclic voltammetry and differential pulse voltammetry in a phosphate buffer solution of pH6.0. The electron-transfer coefficient (α), electron transfer number (n), and electrode reaction rate constant (Κs) were calculated as 0.78, 0.73, and 4.63s -1 , respectively. Under the optimized conditions, the sensor based on magnetic functionalized reduced graphene oxide/Nafion showed a linear voltammetric response to the lobetyolin concentration at 1.0×10 -7 to 1.0×10 -4 mol/L with detection limit (S/N=3)of 4.3×10 -8 mol/L. The proposed sensor also displayed acceptable reproducibility, long-term stability, and high selectivity, and performs well for analysis of lobetyolin in real samples. The voltammetric sensor was successfully applied to detect lobetyolin in Codonopsis pilosula with recovery values in the range of 96.12%-102.66%. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. The electrochemistry of SIMFUEL in dilute alkaline hydrogen peroxide solutions (United States)

    Goldik, Jon

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

  7. 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)


    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.

  8. Splitting Water by Electrochemistry and Artificial Photosynthesis: Excellent Science but a Nightmare of Translation? (United States)

    Antonietti, Markus; Savateev, Alexandr


    Water splitting to its elements, either by electrochemistry or by solar light, is among the most covered areas in nanostructured functional materials. This personal account article analyzes potential downstream translation problems and reviews alternative chemistries with a potential higher return. Liberation of oxygen for accepting the holes is a kinetically demanding half reaction afflicted with kinetic hindrances and high overpotentials, while at the same time no marketable value is created (atmospheric oxygen is free to use). In spite of exciting science created, application in real industrial set-ups is currently impossible, and possible funding promises to contribute to a sustainable society become a debt difficult to return. We discuss possible alternative targets of (photo)electrochemistry as entry points where chemical value products and technical oxidants are created, with partially greater ease, lower losses, and higher benefits. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

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


    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.


    Electrochemistry on graphene is of particular interest due to graphene?s high surface area, high electrical conductivity and low interfacial capacitance. Because the graphene Fermi level can be probed by its strong Raman signal, information on the graphene doping can be obtained which in turn can provide information on adsorbed atoms or molecules. For this paper, the adsorption analysis was successfully performed using three electroactive substances with different electrode interaction mechan...

  11. Some Applications of Electrochemistry in Biomedical Chemistry. Emphasis on the Correlation of Electrochemical and Bioactive Properties


    Abreu, Fabiane C. de; Ferraz, Patrícia A. de L.; Goulart, Marília O. F.


    This review summarises some of the more relevant achievements in the correlation between electrochemical processes and parameters and bioactive properties, mainly related to cancer and tropical diseases. Despite the broad range of possibilities and the complexity of cell/tissue/extracell chemistry, it is possible to rationalise the role of electrochemistry in few basic theoretical frameworks, mainly, the one based on electron transfer-oxidative stress and in situ generation of toxic species, ...

  12. From mercury to nanosensors: Past, present and the future perspective of electrochemistry in pharmaceutical and biomedical analysis. (United States)

    Ozkan, Sibel A; Uslu, Bengi


    Polarography was the first developed automated method of voltage-controlled electrolysis with dropping mercury electrode (DME). Then, hanging mercury drop and static mercury drop electrodes were added as an alternative indicator electrode. In this way, polarography turned formally into voltammetry with mercury electrodes in the electroreduction way. Solid electrodes such as noble metal and carbon based electrodes can be used for the investigation of the compounds for both oxidation and reduction directions, which is called voltammetry. The voltammetric and polarographic techniques are more sensitive, reproducible, and easily used electroanalytical methods that can be alternative to more frequently used separation and spectrometric methods. Furthermore, in some cases there is a relationship between voltammetry and pharmaceutical samples, and the knowledge of the mechanism of their electrode reactions can give a useful clue in elucidation of the mechanism of their interaction with living cells. The voltammetric and polarographic analysis of drugs in pharmaceutical preparations are by far the most common use of electrochemistry for analytical pharmaceutical problems. Recent trends and challenges in the electrochemical methods for the detection of DNA hybridization and pathogens are available. Low cost, small sample requirement and possibility of miniaturization justifies their increasing development. Copyright © 2016 Elsevier B.V. All rights reserved.

  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


    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. Highlights of the Spectroscopy, Photochemistry and Electrochemistry of [M(CO)4(.alfa.-diimine)] Complexes, M=Cr, Mo, W

    Czech Academy of Sciences Publication Activity Database

    Vlček, Antonín


    Roč. 230, - (2002), s. 225-242 ISSN 0010-8545 R&D Projects: GA MŠk OC D14.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : spectroscopy * electrochemistry * photochemistry Subject RIV: CG - Electrochemistry Impact factor: 5.853, year: 2002

  15. 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


    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


    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 ...

  17. 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...

  18. Human sulfite oxidase electrochemistry on gold nanoparticles modified electrode. (United States)

    Frasca, Stefano; Rojas, Oscar; Salewski, Johannes; Neumann, Bettina; Stiba, Konstanze; Weidinger, Inez M; Tiersch, Brigitte; Leimkühler, Silke; Koetz, Joachim; Wollenberger, Ulla


    The present study reports a facile approach for sulfite biosensing, based on enhanced direct electron transfer of a human sulfite oxidase (hSO) immobilized on a gold nanoparticles modified electrode. The spherical core shell AuNPs were prepared via a new method by reduction of HAuCl(4) with branched poly(ethyleneimine) in an ionic liquids resulting particles with a diameter less than 10nm. These nanoparticles were covalently attached to a mercaptoundecanoic acid modified Au-electrode where then hSO was adsorbed and an enhanced interfacial electron transfer and electrocatalysis was achieved. UV/Vis and resonance Raman spectroscopy, in combination with direct protein voltammetry, are employed for the characterization of the system and reveal no perturbation of the structural integrity of the redox protein. The proposed biosensor exhibited a quick steady-state current response, within 2 s, a linear detection range between 0.5 and 5.4 μM with a high sensitivity (1.85 nA μM(-1)). The investigated system provides remarkable advantages in the possibility to work at low applied potential and at very high ionic strength. Therefore these properties could make the proposed system useful in the development of bioelectronic devices and its application in real samples. Copyright © 2011 Elsevier B.V. All rights reserved.

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

    DEFF Research Database (Denmark)

    Zhang, Ling; Ulstrup, Jens; Zhang, Jingdong

    . Hemin itself also acts as catalyst in electrochemical reduction of dioxygen and other small inert molecules suchas nitrogen monoxide, and in electrochemiluminescent detection of dioxygen, peroxide, DNA, and proteins. л-л interactions of hemin with carbon materials have been broadly studied. Hemin...... 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...

  20. Chemical physics of electroactive materials - the oft-overlooked faces of electrochemistry. (United States)

    Kostiuchenko, Zinaida A; Glazer, Piotr J; Mendes, Eduardo; Lemay, Serge G


    Electroactive materials and their applications are enjoying renewed attention, in no small part motivated by the advent of nanoscale tools for their preparation and study. While the fundamentals of charge and mass transport in electrolytes on this scale are by and large well understood, their interplay can have subtle manifestations in the more complex situations typical of, for example, integrated microfluidics-based applications. In particular, the role of faradaic processes is often overlooked or, at best, purposefully suppressed via experimental design. In this introductory article we discuss, using simple illustrations from our laboratories, some of the manifestations of electrochemistry in electroactive materials.

  1. 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.


    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

  2. Chrono-potentiometry by chemical re-dissolution - Electrochemistry in two phase medium

    International Nuclear Information System (INIS)

    Chivot, Jacques


    In this document which comprises two research thesis, the first one addresses the technique of chrono-potentiometry by chemical re-dissolution (or potentiometric stripping analysis). The author, after a presentation of this technique, reports the search for relationships which govern this analytical technique with respect to diffusion transport regimes imposed to species involved in the pre-concentration and chemical re-dissolution stages. The second research thesis addresses dispersed media like emulsions, micro-emulsions and micellar solutions which are interesting potential applications in organic electrochemistry. The author recalls some properties of tensio-active compounds, and then describes electrochemical investigations and electro-synthesis performed within these media

  3. Treatment of effluent at the Saclay Centre d'Etudes Nucleaires (1960)

    International Nuclear Information System (INIS)

    Wormser, G.


    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) [fr

  4. 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


    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.

  5. 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


    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...

  6. Merits of online electrochemistry liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS). (United States)

    Looi, Wen Donq; Brown, Blake; Chamand, Laura; Brajter-Toth, Anna


    A new online electrochemistry/liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS) system with a simple electrochemical thin-layer flow-through cell was developed and tested using N,N-dimethyl-p-phenylenediamine (DMPA) as a model probe. Although oxidation of DMPA is observed as a result of ionization of LS in positive ion mode LS DESI, application of voltage to the online electrochemical (EC) cell in EC/LS DESI MS increases yields of oxidation products. An advantage of LS DESI MS is its sensitivity in aqueous electrolyte solutions, which improves efficiency of electrochemical reactions in EC/LS DESI MS. In highly conductive low pH aqueous buffer solutions, oxidation efficiency is close to 100%. EC/ESI MS typically requires mixed aqueous/organic solvents and low electrolyte concentrations for efficient ionization in MS, limiting efficiency of electrochemistry online with MS. Independently, the results verify higher electrochemical oxidation efficiency during positive mode ESI than during LS DESI.

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

    International Nuclear Information System (INIS)

    Sadoway, D.R.


    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

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

    International Nuclear Information System (INIS)

    Uchida, Shunsuke


    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)

  9. Understanding oxygen electrochemistry in aprotic LiO2 batteries

    Directory of Open Access Journals (Sweden)

    Liang Wang


    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

  10. 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)


    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)

  11. Impact of Interactive Multimedia Module with Pedagogical Agents on Students' Understanding and Motivation in the Learning of Electrochemistry (United States)

    Osman, Kamisah; Lee, Tien Tien


    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…

  12. 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


    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

  13. 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.


    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 * Kinetics of thermal decomposition * Electrochemistry Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.653, year: 2015

  14. Etude comparative de deux produits de neem (huile et poudre) sur ...

    African Journals Online (AJOL)

    Etude comparative de deux produits de neem (huile et poudre) sur les stades préimaginaux du moustique Culex quinquefasciatus(Diptera : Culicidae) ... for nymphs only contact effects are showed. Neem oil formulated 1 % appears more effective than neem powder 0.3 % for mosquitoes control in aquatic environment.

  15. Etude morphologique d'un cas de femme XY avec dysgénésie ...

    African Journals Online (AJOL)

    Mots clés : Etude morphologique, femme XY, dysgénésie gonadique pure. The authors describe the morphological features of a twenty years old female, without ambiguous genitalia, presenting a 46,XY karyotype, normal female external genitalia and gonadal dysgenesis. She has an android type of morpho dysplasia and ...

  16. English Department Reforms at the Hautes Etudes Commerciales: Entering the Nineties. (United States)

    Shanahan, Daniel


    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)

  17. 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 ...

  18. 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, ...

  19. Etude de l'influence des modes de transformation sur les teneurs en ...

    African Journals Online (AJOL)

    Etude de l'influence des modes de transformation sur les teneurs en lycopène de quatre variétés de tomates de la région du nord du Burkina Faso. I Sawadogo, M Koala, C Dabire, LP Ouattara, VBEJT Bazie, A Hema, C Gnoula, E Pale, RHC Nebie ...

  20. Etude comparée des paramètres agromorphologiques de dix (10 ...

    African Journals Online (AJOL)

    Etude comparée des paramètres agromorphologiques de dix (10) variétés de patate douce ( Ipomoea batatas (L.) Lam cultivées au champ dans deux (2) conditions climatiques au Tchad et au Burkina Faso.

  1. 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 ...

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

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

    International Nuclear Information System (INIS)


    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

  4. 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


    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)

  5. Semiconductor electrochemistry

    CERN Document Server

    Memming, Rüdiger


    Providing both an introduction and an up-to-date survey of the entire field, this text captivates the reader with its clear style and inspiring, yet solid presentation. The significantly expanded second edition of this milestone work is supplemented by a completely new chapter on the hot topic of nanoparticles and includes the latest insights into the deposition of dye layers on semiconductor electrodes. In his monograph, the acknowledged expert Professor Memming primarily addresses physical and electrochemists, but materials scientists, physicists, and engineers dealing with semiconductor technology and its applications will also benefit greatly from the contents.

  6. Semiconductor electrochemistry

    National Research Council Canada - National Science Library

    Memming, Rüdiger


    ... . . . . . . . . . . . . . . . . . . . . . . . . . . . Carrier Transport Phenomena . . . . . . . . . . . . . . . . . . . . . . . . Excitation and Recombination of Charge Carriers . . . . . . . . . . . . Fermi Levels...

  7. Boundary asymptotics for a non-neutral electrochemistry model with small Debye length (United States)

    Lee, Chiun-Chang; Ryham, Rolf J.


    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.

  8. In-situ Raman spectroscopy to elucidate the influence of adsorption in graphene electrochemistry. (United States)

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


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

  9. Regal electrochemistry: British 5 pence coins provide useful metallic macroelectrode substrates. (United States)

    Tan, Fang; Smith, Jamie P; Kampouris, Dimitrios K; Kamieniak, Joanna; Banks, Craig E


    The utilisation of British Currency (GBP) as an electrode substrate is demonstrated for the first time. Termed Regal electrochemistry, a 5 pence (5p) coin (GBP) is electrically wired using a bespoke electrochemical cell and is electrochemically characterised using the outer-sphere redox probe hexaammineruthenium(III) chloride. The electroanalytical utility of the 5p coin electrode is demonstrated towards the novel, proof-of-concept sensing of lead(II) ions using square-wave voltammetry in model buffer solutions over the linear range 5-2000 nM exhibiting a limit of detection (3σ) of 1.97 nM. Interestingly, the actual cost of the electrode is 2.5 pence (GBP) since both sides of the coins can be utilised and provide a cheap yet reproducible and disposable metallic electrode substrate that is electrochemically useful.

  10. Ubiquitous trisulfur radical anion: fundamentals and applications in materials science, electrochemistry, analytical chemistry and geochemistry. (United States)

    Chivers, Tristram; Elder, Philip J W


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

  11. Nanopore Electrochemistry: A Nexus for Molecular Control of Electron Transfer Reactions (United States)


    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

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

    Directory of Open Access Journals (Sweden)

    Kaiyu Fu


    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.

  13. In Situ, Real-Time Visualization of Electrochemistry Using Magnetic Resonance Imaging. (United States)

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


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

  14. Electrochemistry Modeling of Proton Exchange Membrane (PEM) Water Electrolysis for Hydrogen Production

    International Nuclear Information System (INIS)

    Meng Ni; Michael KH Leung; Dennis YC Leung


    An electrochemistry model was developed to analyse the J-V characteristics of a Proton Exchange Membrane (PEM) water electrolyzer for hydrogen production. The Butler-Volmer equation and water transport characteristics through electrolyte membrane were employed to simulate the electrode activation over-potential and membrane ohmic over-potential, respectively. The modeling results are found to agree reasonably well with experimental data published in the literature. The parametric simulations show that the ohmic over-potential is relatively small with typical water content in the membrane. Compared with the cathode over-potential, the anode over-potential is more significant and constitutes the major source of voltage loss. The high anode over-potential is due to the relatively slow oxidation kinetics, which is related to anode material property and microstructure. This model can be integrated with a photovoltaic or wind turbine model to predict the performance of sustainable hydrogen production systems and optimise their designs. (authors)

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

    Directory of Open Access Journals (Sweden)

    Suzanne Lunsford


    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 (United States)

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


    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. Dynamic Electrochemistry Corrects for Hematocrit Interference on Blood Glucose Determinations with Patient Self-Measurement Devices (United States)

    Musholt, Petra B; Schipper, Christina; Thomé, Nicole; Ramljak, Sanja; Schmidt, Marc; Forst, Thomas; Pfützner, Andreas


    Background It has been demonstrated that dynamic electrochemistry can be used to correct blood glucose measurement results for potentially interfering conditions, such as humidity, hematocrit (HCT) variations, and ascorbic acid. The purpose of this laboratory investigation was to assess the potential influence of hematocrit variations on a variety of blood glucose meters applying different measurement technologies. Methods Venous heparinized whole blood was drawn, immediately aliquoted, and manipulated to contain three different blood glucose concentrations (80, 155, and 310 mg/dl) and five different hematocrit levels (25%, 37%, 45%, 52%, and 60%). After careful oxygenation to normal blood oxygen pressure, each of the resulting 15 different samples was measured 8 times with the following devices: BGStar, Contour, Accu-Chek Aviva, Accu-Chek Aviva Nano, Breeze 2, Precision Xceed, OneTouch Ultra 2, OneTouch Verio, FreeStyle Freedom Lite, Glucocard G+, GlucoMen LX, GlucoMen GM, and StatStrip [point-of-care (POC) device]. Cobas (Roche Diagnostics, glucose hexokinase method) served as laboratory plasma reference method. Stability to hematocrit influence was assumed when less than 10% bias occurred between the highest and lowest hematocrit levels when analyzing mean deviations for all three glucose concentrations. Results Besides the POC StatStrip device, which is known to measure and correct for hematocrit (resulting in hematocrit variations occur in daily routine (e.g., because of smoking, exercise, hypermenorrhea, pregnancy, stay in mountains, and hemodialysis), our results may encourage use of meters with stable performance under these conditions. Dynamic electrochemistry as used in the BGStar device (sanofi-aventis) appears to be an effective technology to correct for potential hematocrit influence on the meter results. PMID:22027312

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

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

    Directory of Open Access Journals (Sweden)

    Sanju Gupta


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

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

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Sanju, E-mail: [Department of Physics and Astronomy, Western Kentucky University, 1906 College Heights Blvd. Bowling Green, KY 42101-3576 (United States); Biotechnology Center, Western Kentucky University, 1906 College Heights Blvd. Bowling Green, KY 42101-3576 (United States); Irihamye, Aline [Gatton Academy of Mathematics and Science in Kentucky, Western Kentucky University, 1906 College Heights Blvd. Bowling Green, KY 42101-3576 (United States)


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

  1. 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


    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)


    Directory of Open Access Journals (Sweden)

    Yucan EKE


    Full Text Available This research is done for attesting the compliance of the etudes in German composer Ernesto Köhler’s op:33 no I-II-III books that are used in high schools of fine arts, with ability to play the flute concertos in high schools of fine arts 12 grade program, in terms of the knowledge – skills and musical functions they cover and also for contributing to learning by matching the etudes and works which are relevant. Etudes and the chosen concertos are analyzed and separated into templates in terms of melody, rhythm and tone for this research. Opinions are taken from the flute lesson instructors of various universities of Turkey to define the melody, technique and rhythm patterns. As a result of the analysis, Köhler op: 33, Book I, Etudes: 2,3,6,7,8,9,10,11,12; Köhler op: 33, Book II, Etudes:1,3,4,5,8,9,10,11; Köhler op: 33, Book III, Etudes: 1, 2, 4, 5, 6, 8; It is determined that the etudes given above in Köhler books are qualified enough to be preparative and instructive for the ability of playing the flute concertos. Some suggestions are given about which etude(s is instructive for which concerto and what kind of benefits could be gained, by this study. Based on the observed results, various suggestions are made about defining and studying the etudes which meet the technical, rhythmic and melodic features of the target concerto.

  3. Cognitive decline is associated with systemic oxidative stress: the EVA study. Etude du Vieillissement Artériel. (United States)

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


    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.

  4. Etude d'un systeme de recuperation et de stockage de chaleur pour un systeme eolien-diesel avec stockage d'air comprime (United States)

    Remillon, Thibaut

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

  5. The role of NH 4 + cations on the electrochemistry of Prussian Blue studied by electrochemical, mass, and color impedance spectroscopy


    Agrisuelas, Jeronimo; Delgado, C.; Gabrielli, Claude; García-Jareño, J. J.; Perrot, Hubert; Sel, Ozlem; Vicente, F.


    "The original publications is available at"; International audience; The role of the ammonium cation on the reversible electrochemistry of Prussian Blue thin films was analyzed through in situ combination of three different impedance techniques. Electrochemical impedance spectroscopy provides information on the electron transfer. Mass impedance spectroscopy allows the exchange of free water, ammonium and proton ions to be elucidated. Color impedance spectroscopy provides ...

  6. 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


    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

  7. 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


    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.)

  8. Etude sur les tendons en materiaux composites et leur application aux ancrages postcontraints (United States)

    Chennouf, Adil

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

  9. 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.


    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.

  10. Etude écologique du Parc National de Mozogo-Gokoro (Cameroun ...

    African Journals Online (AJOL)

    Etude écologique du Parc National de Mozogo-Gokoro (Cameroun): prospections préliminaires de la flore ligneuse et du sol pour sa conservation et son aménagement. ... d'aménagement. Mots clés : Pré-inventaire, diversité compositionnelle, structure, écosystème de référence, menaces anthropiques, aire protégée ...

  11. Etude des boues résiduaires de la station de traitement des eaux de ...

    African Journals Online (AJOL)

    Etude des boues résiduaires de la station de traitement des eaux de Ziga et examen de leur possible valorisation pour la confection de barrières étanches. ... pour caractériser la cohérence et la capacité de faire couler la matière dans les procédés industriels et sur les mesures de filtration de la perméabilité du gâteau

  12. Etude de conception d'un simulateur de commande numérique en ...

    African Journals Online (AJOL)

    or Register. DOWNLOAD FULL TEXT Open Access DOWNLOAD FULL TEXT Subscription or Fee Access. Etude de conception d'un simulateur de commande numérique en tournage. K. A. Kasségné, AS Ajavon, C Carton, A Pouyo. Abstract. (J. de la Recherche Scientifique de l'Université de Lomé, 2000, 4(2): 169-180) ...

  13. Singing as a Therapeutic Agent, inThe Etude, 1891-1949. (United States)



    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.

  14. Carbonyl Functionalized Single-Walled Carbon Nanotube-Hb Crosslinked Network: A Novel Platform for Studying Bio-Electrochemistry and Electrocatalysis of Hemoglobin. (United States)

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


    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.

  15. Extended Abstracts, International Society of Electrochemistry (36th) Held at Salamanca, Spain on 23-28 September 1985. (United States)



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

    KAUST Repository

    Samu, Gergely F.


    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.

  17. 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


    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.

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

    International Nuclear Information System (INIS)

    Francis, A.M.A.


    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

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

    International Nuclear Information System (INIS)

    Uchida, Shunsuke


    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.)

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

    Directory of Open Access Journals (Sweden)

    De Paoli Marco-A.


    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.

  1. Combinatorial electrochemistry using metal nanoparticles: from proof-of-concept to practical realisation for bromide detection. (United States)

    Sljukić, Biljana; Baron, Ronan; Salter, Chris; Crossley, Alison; Compton, Richard G


    Principles and practical application of combinatorial electrochemistry in search for new electroactive materials in electroanalysis have been explored. Nanoparticles of three different metals: silver, gold and palladium have been independently synthesized on the glassy carbon spherical powder surface by electroless deposition process and characterized using both spectroscopic and electrochemical techniques. These three materials were then combined together onto basal plane pyrolytic graphite electrode surface and the application of the combinatorial approach to find the electrode material for bromide detection as model target analyte was demonstrated. The component electroactive for bromide detection was next identified and it was found that silver nanoparticles were the active ones. A composite electrode based on silver nanoparticle modified glassy carbon powder and epoxy resin was then fabricated and it was found to allow accurate determination of bromide. The electroactivity for the bromide determination of the composite electrode was compared with that of a bulk silver electrode and it was shown that the composite electrode is very efficient with a comparable electroactivity with only a portion of precious metals being used for its construction.

  2. 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


    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.

  3. 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


    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)

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

    International Nuclear Information System (INIS)

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


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

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

    CERN Document Server

    Scholz, Fritz; Gulaboski, Rubin; Schröder, Uwe


    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...

  6. Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions (United States)


    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

  7. Theoretical and Experimental Methods in Hypersonic Flows (Les Methodes Theoriques et Experimentales pour l’Etude Des Ecoulements Hypersoniques) (United States)


    eropaceReserchIngenieros Aeronauticos InRC.ut Bldg M-osac 10eac Departamento de Mecanica de Fluidos MntrealdgRoad Plaza del Cardenal Cisneros 3 Ottawa K I A 1)R6...PROCEEDINGS 514 OELECTE f Theoretical and A U Experimental Methods in A Hypersonic Flows (Les Methodes Th6oriques et Experimentales pour 1’Etude des ...CONFERENCE PROCEEDINGS 514 Theoretical and - Experimental Methods in Hypersonic Flows .... t ,Z (Les Mthodes Th~oriques et Exp6rimentales pour I’Etude des

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

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


    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.

  9. Enhanced direct electrochemistry of glucose oxidase and biosensing for glucose via synergy effect of graphene and CdS nanocrystals. (United States)

    Wang, Kun; Liu, Qian; Guan, Qing-Meng; Wu, Jun; Li, He-Nan; Yan, Jia-Jia


    Integrating graphene-based composites with enzyme provides a potent strategy to enhance biosensor performance due to their unique physicochemical properties. Herein we report on the utilization of graphene-CdS (G-CdS) nanocomposite as a novel immobilization matrix for the enzymes, which glucose oxidase (GOD) was chosen as model enzyme. In comparison with the graphene sheet and CdS nanocrystal, G-CdS nanocomposite exhibited excellent electron transfer properties for GOD with the rate constant (k(s)) of 5.9 s(-1) due to the synergy effect of graphene sheet and CdS nanocrystals. Further, based on the decrease of the electrocatalytic response of the reduced form of GOD to dissolved oxygen, the obtained glucose biosensor displays satisfactory analytical performance over an acceptable linear range from 2.0 to 16 mM with a detection limit of 0.7 mM, and also prevents the effects of interfering species, which is suitable for glucose determination by real samples. These results mean that this immobilization matrix not only can be used for immobilizing GOD, but also can be extended to other enzymes and bioactive molecules, thus providing a promising platform for the development of biosensors. Copyright © 2010 Elsevier B.V. All rights reserved.

  10. Synthesis, electrochemistry, and electrogenerated chemiluminescence of two BODIPY-appended bipyridine homologues. (United States)

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


    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.

  11. Synthesis, Electrochemistry and Electrogenerated Chemiluminesce of two BODIPY-Appended Bipyridine Homologues (United States)

    Qi, Honglan; Teesdale, Justin J.; Pupillo, Rachel C.


    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

  12. Endogenous minerals have influences on surface electrochemistry and ion exchange properties of biochar. (United States)

    Zhao, Ling; Cao, Xinde; Zheng, Wei; Wang, Qun; Yang, Fan


    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.

  13. 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)


    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.

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

    International Nuclear Information System (INIS)

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


    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

  15. Immobilization of alkynyl functionalized manganese phthalocyanine via click electrochemistry for electrocatalytic oxygen evolution reaction. (United States)

    Öztaş, B; Akyüz, D; Koca, A


    Peripherally and non-peripherally terminal alkynyl substituted manganese phthalocyanines (MnPc) were synthesized and characterized and then used as functional materials in modified electrodes. MnPcs were substituted with alkynyl groups, which are reactive moieties in click electrochemistry (CEC) reactions. Mn(iii) cations were incorporated into the cavity of the Pc ring in order to increase the redox activity of the complexes. Electrochemical characterizations of the complexes were determined by voltammetric and in situ spectroelectrochemical measurements in order to determine their possible technological applications. MnPc complexes illustrated five redox couples and these redox couples were assigned as [Cl-Mn III Pc 2- ]/[Cl-Mn II Pc 2- ] 1- , [Cl-Mn II Pc 2- ] 1- /[Cl-Mn I Pc 2- ] 2- , [Cl-Mn I Pc 2- ] 2- /[ Cl-Mn I Pc 3- ] 3- , and [Cl-Mn III Pc 2- ]/[Cl-Mn III Pc 1- ] 1+ redox processes. The position of the substituents affected the mechanism of the redox reactions and influenced the tendency to react with the molecular oxygen. Moreover, changing the position of the substituents slightly influenced the peak potentials and reversibility of the redox processes. For the applications, modified electrodes (ITO/PANI-N 3 -MnPc and GCE/PANI-N 3 -MnPc) were constructed with CEC reaction between azido functionalized polyaniline (PANI-N 3 ) and terminally alkynyl substituted MnPcs and these electrodes. Voltammetric characterizations of the modified electrodes illustrated suitable redox activity and conductivity for the practical applications. Finally, the GCE/PANI-N 3 -MnPc electrode was tested as a potential electrocatalyst for water splitting reaction. Although the GCE/PANI-N 3 -MnPc electrode did not catalyze the hydrogen evolution reaction (HER), it significantly catalyzed the oxygen evolution reaction (OER) in aqueous solution.

  16. Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries. (United States)

    Lin, Feng; Liu, Yijin; Yu, Xiqian; Cheng, Lei; Singer, Andrej; Shpyrko, Oleg G; Xin, Huolin L; Tamura, Nobumichi; Tian, Chixia; Weng, Tsu-Chien; Yang, Xiao-Qing; Meng, Ying Shirley; Nordlund, Dennis; Yang, Wanli; Doeff, Marca M


    Rechargeable battery technologies have ignited major breakthroughs in contemporary society, including but not limited to revolutions in transportation, electronics, and grid energy storage. The remarkable development of rechargeable batteries is largely attributed to in-depth efforts to improve battery electrode and electrolyte materials. There are, however, still intimidating challenges of lower cost, longer cycle and calendar life, higher energy density, and better safety for large scale energy storage and vehicular applications. Further progress with rechargeable batteries may require new chemistries (lithium ion batteries and beyond) and better understanding of materials electrochemistry in the various battery technologies. In the past decade, advancement of battery materials has been complemented by new analytical techniques that are capable of probing battery chemistries at various length and time scales. Synchrotron X-ray techniques stand out as one of the most effective methods that allow for nearly nondestructive probing of materials characteristics such as electronic and geometric structures with various depth sensitivities through spectroscopy, scattering, and imaging capabilities. This article begins with the discussion of various rechargeable batteries and associated important scientific questions in the field, followed by a review of synchrotron X-ray based analytical tools (scattering, spectroscopy, and imaging) and their successful applications (ex situ, in situ, and in operando) in gaining fundamental insights into these scientific questions. Furthermore, electron microscopy and spectroscopy complement the detection length scales of synchrotron X-ray tools and are also discussed toward the end. We highlight the importance of studying battery materials by combining analytical techniques with complementary length sensitivities, such as the combination of X-ray absorption spectroscopy and electron spectroscopy with spatial resolution, because a sole

  17. 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


    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

  18. Etude de la diversité, de l'endémisme et de la distribution spatiale ...

    African Journals Online (AJOL)

    Etude de la diversité, de l'endémisme et de la distribution spatiale des Rubiaceae de Côte d'Ivoire. Fatou Nanou Tuo, Kouao Jean Koffi, Akossoua Faustine Kouassi, Moussa Kone, Bakayoko Adama, Jan Bogaert ...

  19. Etude de la qualité organoleptique de trois variétés de mangues ...

    African Journals Online (AJOL)

    Etude de la qualité organoleptique de trois variétés de mangues Amélie , Lippens , Brooks séchées au cours du stockage par technique de brunissement enzymatique des peroxydases (POD) et des polyphénoloxydases (PPO)

  20. 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.

  1. 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


    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)

  2. 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


    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

  3. Roles of surface chemistry on safety and electrochemistry in lithium ion batteries. (United States)

    Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil


    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

  4. 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


    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

  5. Electrochemistry of Chromium(0) – Aminocarbene Complexes. The use of intramolecular interaction LFER for characterization of the oxidation and reduction centre of the complex

    Czech Academy of Sciences Publication Activity Database

    Hoskovcová, I.; Roháčová, J.; Meca, L.; Tobrman, T.; Dvořák, D.; Ludvík, Jiří


    Roč. 50, - (2005), s. 4911-4915 ISSN 0013-4686 R&D Projects: GA ČR(CZ) GA203/04/0487 Institutional research plan: CEZ:AV0Z40400503 Keywords : electroreduction * electrooxidation * cyclic voltammetry Subject RIV: CG - Electrochemistry Impact factor: 2.453, year: 2005

  6. 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.


    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

  7. 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


    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

  8. High Performance Liquid Chromatography-Electrochemistry-Electrospray Ionization Mass Spectrometry (HPLC/EC/ESI-MS) for Detection and Characterization of Roscovitine Oxidation Products

    Czech Academy of Sciences Publication Activity Database

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


    Roč. 23, č. 12 (2011), s. 2898-2905 ISSN 1040-0397 R&D Projects: GA MŠk ED0007/01/01; GA ČR GA301/08/1649 Keywords : Electrochemistry * Mass spectrometry * R-roscovitine Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.872, year: 2011

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

    International Nuclear Information System (INIS)

    Debiesse, J.


    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

  10. 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


    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

  11. L'etude de l'InP et du GaP suite a l'implantation ionique de Mn et a un recuit thermique (United States)

    Bucsa, Ioan Gigel

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

  12. 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


    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

  13. 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


    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

  14. Single nanowire electrode electrochemistry of silicon anode by in situ atomic force microscopy: solid electrolyte interphase growth and mechanical properties. (United States)

    Liu, Xing-Rui; Deng, Xin; Liu, Ran-Ran; Yan, Hui-Juan; Guo, Yu-Guo; Wang, Dong; Wan, Li-Jun


    Silicon nanowires (SiNWs) have attracted great attention as promising anode materials for lithium ion batteries (LIBs) on account of their high capacity and improved cyclability compared with bulk silicon. The interface behavior, especially the solid electrolyte interphase (SEI), plays a significant role in the performance and stability of the electrodes. We report herein an in situ single nanowire atomic force microscopy (AFM) method to investigate the interface electrochemistry of silicon nanowire (SiNW) electrode. The morphology and Young's modulus of the individual SiNW anode surface during the SEI growth were quantitatively tracked. Three distinct stages of the SEI formation on the SiNW anode were observed. On the basis of the potential-dependent morphology and Young's modulus evolution of SEI, a mixture-packing structural model was proposed for the SEI film on SiNW anode.

  15. Fast single run of vanilla fingerprint markers on microfluidic-electrochemistry chip for confirmation of common frauds. (United States)

    Avila, Mónica; Zougagh, Mohammed; Escarpa, Alberto; Ríos, Angel


    A new strategy based on the fast separation of the fingerprint markers of Vanilla planifolia extracts and vanilla-related samples on microfluidic-electrochemistry chip is proposed. This methodology allowed the detection of all required markers for confirmation of common frauds in this field. The elution order was strategically connected with sequential sample screening and analyte confirmation steps, where first ethyl vanillin was detected to distinguish natural from adultered samples; second, vanillin as prominent marker in V. planifolia, but frequently added in its synthetic form; and third, the final detection of the fingerprint markers (p-hydroxybenzaldehyde, vanillic acid, and p-hydroxybenzoic acid) of V. planifolia with confirmation purposes. The reliability of the proposed methodology was demonstrated in the confirmation the natural or non-natural origin of vanilla in samples using V. planifolia extracts and other selected food samples containing this flavor.

  16. Using electrochemistry - total internal refection imaging ellipsometry to monitor biochemical oxygen demand on the surface tethered polyelectrolyte modified electrode (United States)

    Liu, Wei; Li, Meng; Lv, Bei'er; Chen, YanYan; Ma, Hongwei; Jin, Gang


    Our previous work has proposed an electrochemistry - total internal reflection imaging ellipsometry (EC-TIRIE) technique to observe the dissolved oxygen (DO) reduction on Clark electrode since high interface sensitivity makes TIRIE a useful tool to study redox reactions on the electrode surface. To amplify the optical signal noise ratio (OSNR), a surface tethered weak polyelectrolyte, carboxylated poly(oligo(ethylene glycol) methacrylate-random- 2-hydroxyethylmethacrylate) (abbreviated as carboxylated poly(OEGMA-r-HEMA)), has been introduced on the electrode surface. Since Clark electrode is widely used in biochemical oxygen demand (BOD) detection, we use this technique to measure BOD in the sample. The dynamic range of the system is from 0 ˜ 25 mg/L. Two samples have been measured. Compared with the conventional method, the deviation of both optical and electrical signals are less than 10%.

  17. Dual reductive/oxidative electrochemistry/liquid chromatography/mass spectrometry: Towards peptide and protein modification, separation and identification. (United States)

    Büter, Lars; Frensemeier, Lisa M; Vogel, Martin; Karst, Uwe


    A new hyphenated technique based on on-line dual (oxidative and reductive) electrochemistry coupled to liquid chromatography and high resolution electrospray mass spectrometry is presented. Two liquid streams are combined, with one containing a disulfide, which is reduced to the respective thiol in an electrochemical cell based on a titanium working electrode. The other stream contains phenol, which is electrochemically activated to benzoquinone on a boron-doped diamond working electrode. Upon combination of the two streams, a Michael addition takes places, leading to the covalent coupling of thiol to quinone. In continuous flow, the reaction mixture is transferred into an injection valve and the products are separated by reversed phase liquid chromatography and detected by electrospray-high resolution mass spectrometry. Proof of concept is demonstrated for low molecular mass disulfides and peptides, but further optimization will be required in future work to achieve efficient protein labelling. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. 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


    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)

  19. 107 Etude des facteurs de variation des prix d'intérêt des matières ...

    African Journals Online (AJOL)


    Imen BELHADJ SLIMEN et Taha NAJAR. Etude des facteurs de variation des prix d'intérêt des matières premières de substitution utilisées dans les aliments concentrés des animaux d'élevage. Imen BELHADJ SLIMEN1,2* et Taha NAJAR1,2. 1Institut National Agronomique de Tunisie, Département Ressources Animales, ...

  20. Etude de la qualité organoleptique de trois variétés de mangues ...

    African Journals Online (AJOL)

    Etude de la qualité organoleptique de trois variétés de mangues Amélie , Lippens , Brooks séchées au cours du stockage par technique de brunissement enzymatique des peroxydases (POD) et des ... Les activités les plus élevées en polyphénoloxydase et en peroxydase étaient respectivement de 19.75×10-3 ± 0.01 et 52.

  1. 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 ...

  2. Etude in vitro de l'activité antibactérienne et antifongique de l'extrait ...

    African Journals Online (AJOL)


    UNR –Journal Etudes Rwandaises– Series C:Life Science & Natural Sciences– August 2009. 12. Tableau 4 : Test de l'activité de l'extrait et fractions à différents degrés de pH. Extrait hydroéthanolique. F2. F3. Souches microbiennes. A B C D E. A B C D E A B C D E. pH : 5. - - - - -. - - - - - - - - - -. pH : 7. - - - - - - - - - - - - - - -.

  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.


    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. Electrochemistry and electrogenerated chemiluminescence of dithienylbenzothiadiazole derivative. Differential reactivity of donor and acceptor groups and simulations of radical cation-anion and dication-radical anion annihilations. (United States)

    Shen, Mei; Rodríguez-López, Joaquín; Huang, Ju; Liu, Quan; Zhu, Xu-Hui; Bard, Allen J


    We report here the electrochemistry and electrogenerated chemiluminescence (ECL) of a red-emitting dithienylbenzothiadiazole-based molecular fluorophore (4,7-bis(4-(4-sec-butoxyphenyl)-5-(3,5-di(1-naphthyl)phenyl)thiophen-2-yl)-2,1,3-benzothiadiazole, 1b). 1b contains two substituted thiophene groups as strong electron donors at the ends connected directly to a strong electron acceptor, 2,1,3-benzothiadiazole, in the center. Each thiophene moiety is substituted in position 2 by 3,5-di(1-naphthyl)phenyl and in position 3 by 4-sec-butoxyphenyl. Cyclic voltammetry of 1b, with scan rate ranging from 0.05 to 0.75 V/s, shows a single one-electron reduction wave (E°(red) = -1.18 V vs SCE) and two nernstian one-electron oxidation waves (E°(1,ox) = 1.01 V, E°(2,ox) = 1.24 V vs SCE). Reduction of the unsubstituted 2,1,3-benzothiadiazole center shows nernstian behavior with E°(red) = -1.56 V vs SCE. By comparison to a digital simulation, the heterogeneous electron-transfer rate constant for reduction, k(r)° = 1.5 × 10(-3) cm/s, is significantly smaller than those for the oxidations, k(o)° > 0.1 cm/s, possibly indicating that the two substituted end groups have a blocking effect on the reduction of the benzothiadiazole center. The ECL spectrum, produced by electron-transfer annihilation of the reduced and oxidized forms, consists of a single peak with maximum emission at about 635 nm, consistent with the fluorescence of the parent molecule. Relative ECL intensities with respect to 9,10-diphenylanthracene are 330% and 470% for the radical anion-cation and radical anion-dication annihilation, respectively. Radical anion (A(-•))-cation (A(+•)) annihilation produced by potential steps shows symmetric ECL transients during anodic and cathodic pulses, while for anion (A(-•))-dication (A(2+•)) annihilation, transient ECL shows asymmetry in which the anodic pulse is narrower than the cathodic pulse. Digital simulation of the transient ECL experiments showed that the

  5. Etude structurale et hydrodynamique de l'Aquifere du continental ...

    African Journals Online (AJOL)

    Face aux pressions exercées sur cet aquifère il est important de faire une caractérisation hydrogéologique visant à mieux connaitre la ressource afin de la pérenniser. L'étude structurale a montré que l'aquifère libre du Continental terminal présente un substratum incliné en direction de l'océan. Les altitudes du substratum ...

  6. Etude rheologique des composites charges de fibres de verre courtes (United States)

    Sepehr, Maryam

    The rheological behavior of short-fiber polypropylene has been studied in shear flow. Because of some restrictions in the measurement and the complex behavior of the matrix, we chose to use model fiber suspensions in two different types of matrix, a Newtonian polybutene and a Boger fluid. The steady-state viscosity of the Newtonian polybutene increased by adding fibers and the behavior of the fiber suspensions essentially remained Newtonian. The Boger fluid was obtained by adding a high molecular weight polyisobutylene to the Newtonian polybutene. The transient behavior of all types of fiber suspensions (with the viscoelastic, the Newtonian and the Boger fluid matrices) in shear flow has been investigated. Following a first deformation, the sample has been sheared in the reverse direction and a viscosity overshoot called the "reverse overshoot" was measured at a larger strain in comparison with the primary viscosity overshoot. The reverse overshoot has been attributed to tumbling of fibers that are not totally aligned with the flow direction even after a very long time. When the flow was reversed, the normal stress difference took initially minimum values and depicted a smaller positive overshoot before reaching the steady-state plateau. Two models have been used to simulate the rheological behavior of fiber suspensions. The first model is based on the Folgar and Tucker equation for fiber motion and Lipscomb constitutive equation. This model describes qualitatively well the transient behavior of fiber suspensions in both forward and reverse direction flows. However, the fiber motions predicted by the model are faster than deducted from the experiments. This was tentatively explained by non-affined deformation and direct contacts with neighboring fibers, reducing fiber rotation. The second model investigated was the extended Jeffery model developed by Grmela et al. (2003) who generalized the Jeffery model, to include fiber-fiber interactions via angular momentum and

  7. Etude des phenomenes dynamiques ultrarapides et des caracteristiques impulsionnelles d'emission terahertz du supraconducteur YBCO (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

  8. Etude numerique du sillage tourbillonnaire d'une eolienne (United States)

    Sibuet Watters, Christophe

    Cette these formalise le concept de la surface actuatrice (SA) et en presente l'implantation dans deux methodes de mecanique des fluides assistee par ordinateur (CFD) bidimensionnelle (2D) et tridimensionnelle (3D), la validation et l'application au probleme de modelisation du sillage tourbillonnaire d'une eolienne. En termes cinetiques, une SA est une nappe tourbillonnaire qui resulte en une discontinuite de vitesse tandis qu'en termes dynamiques, elle est associee a un systeme de forces dont la composante dans la direction normale a la SA resulte en une discontinuite de pression. Les methodes CFD utilisees sont des methodes aux volumes finis, adaptees pour prendre en compte l'action de la SA sur l'ecoulement. L'approche de la SA est validee pour des problemes 2D: aile infinie et disque actuateur, ainsi que pour le probleme 3D de l'aile en translation (aile effilee), avant d'etre appliquee a plusieurs eoliennes.

  9. 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:


    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.

  10. 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)


    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)

  11. 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


    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

  12. Electrochemistry and Electrogenerated Chemiluminescence of 1,3,5-Tri(anthracen-10-yl)-benzene-Centered Starburst Oligofluorenes. (United States)

    Qi, Honglan; Zhang, Chengxiao; Huang, Zhi; Wang, Lei; Wang, Weina; Bard, Allen J


    The electrochemistry and electrogenerated chemiluminescence (ECL) of three 1,3,5-tri(anthracen-10-yl)-benzene-centered starburst oligofluorenes (T1-T3) are reported in this paper. The compounds T1-T3 contain 1,3,5-tri(anthracen-10-yl)-benzene as a core with fluorene as an arm from monofluorene to trifluorene groups (n = 1-3), generating a rigid three-dimensional structure. The electrochemical behaviors of these compounds are likely to be tuned by the fluorene arms. In cyclic voltammograms, both the oxidation and reduction of T1 and T2 are characterized by three reversible one-electron transfers from the core while the oxidation and reduction of T3 are characterized by six reversible one-electron transfers from the core and the arms in acetonitrile:benzene (v:v = 1:1) solvent. The second oxidation and reduction waves of T1 show three reversible one-electron transfers from three fluorene arms, while the second and third oxidation and reduction waves of T2 and T3 exhibit three reversible one-electron transfers from the six fluorene arms. The multiple electron transfers in one molecule are confirmed by chronoamperometry at an ultramicroelectrode, simulations and DFT calculations. The T1-T3 compounds display strong absorption in UV-vis and blue fluorescence emission. Strong blue ECL emissions can be generated from T1, T2 and T3 under ion annihilation condition, which is assigned as S-route.

  13. 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.


    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

  14. Impact of Soil Composition and Electrochemistry on Corrosion of Rock-cut Slope Nets along Railway Lines in China (United States)

    Chen, Jiao; Chen, Zhaoqiong; Ai, Yingwei; Xiao, Jingyao; Pan, Dandan; Li, Wei; Huang, Zhiyu; Wang, Yumei


    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.

  15. Electrochemistry in aqueous solution at high temperature and under pressure: study of nickel in a highly alkaline environment

    International Nuclear Information System (INIS)

    Forestier, Michel


    This research thesis reports the study of the corrosion resistance and anodic behaviour of various metals and alloys used in conventional thermal or nuclear power stations, more particularly the case of nickel in a highly alkaline environment (KOH 5 N) which is widely used for hydrogen production by water electrolysis. The author studied the influence of temperature and pressure on the electrochemical behaviour of nickel, and more particularly the first-oxidation kinetics. The report discusses the physicochemical and thermodynamic properties of aqueous systems at high temperature and under pressure, presents the general techniques of high-temperature electrochemistry, describes the experimental installation, and reports the development of a reference electrode which can operate in those experimental conditions. The author reports the study of the electrochemical behaviour of nickel in alkaline environment and at high temperature, reports a surface analysis performed by Auger spectroscopy, electron spectroscopy for chemical analysis or ESCA, and scanning electronic microscopy, reports the study of the electrochemical behaviour of nickel in a potassium hydroxide solution under normal temperature and pressure, but also in acid environment. Results are interpreted with respect to temperature [fr

  16. A battery model that fully couples mechanics and electrochemistry at both particle and electrode levels by incorporation of particle interaction (United States)

    Wu, Bin; Lu, Wei


    This paper develops a multi-scale mechanical-electrochemical model which enables fully coupled mechanics and electrochemistry at both particle and electrode levels. At the particle level, solid diffusion is modeled using a generalized chemical potential to capture the effects of mechanical stress and phase transformation. At the electrode level, the stress arising from particle interaction is incorporated in a continuum model. This particle interaction stress is in addition to the traditional concept of intercalation stress inside isolated particles. The particle and continuum electrode levels are linked by the particle interaction stress as loads on the particle surface, and by consideration of stress on the electrochemical reaction rate on the particle surface. The effect of mechanical stress on electrochemical reaction results in a stress-dependent over-potential between particle and electrolyte. Stress gradient in an electrode leads to inhomogeneous intercalation/deintercalation currents for particles depending on their interaction stress with neighbors, resulting in stress gradient induced inhomogeneous state of charge. Conversely, non-uniform intercalation/deintercalation currents in an electrode lead to stress between particles. With this model we have an important finding: an electrochemically inactive region in an electrode causes stress built-up. This model provides a powerful tool to address various problems such as fracture in-between particles.

  17. Metal (Co, Fe) tribenzotetraazachlorin-fullerene conjugates: impact of direct p-bonding on the redox behaviour and oxygen reduction reaction

    CSIR Research Space (South Africa)

    Ozoemena, KI


    Full Text Available on the solution electrochemistry of these metallophthalocyanine (MPc)complexes. The more electron-withdrawing C60 substituent suppressed ORR compared to the –SO2Bu Metal (Co, Fe) tribenzotetraazachlorin–fulleren p-bonding on the redox behaviour and oxyge...., Metal (Co, Fe) tribenzotetraa behaviour and oxygen reduction reaction, Electrochem. Commun. (2009), doi:1 zachlorin–fullerene conjugates: Impact of direct p-bonding on the redox 0.1016/j.elecom.2009.04.011 ...

  18. 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


    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...... (hexadecanethiol, MHD) or hydrophilic (mercapto-hexadecanoic acid, MHDA) end groups. The voltammetric reductive desorption (RD) peaks of the thiol-based SAMs in the absence and presence of biofilms and growth medium was in focus as a sensitive probe of the SAM local environment.AFM showed that S. mutans had grown...... with growth medium or of the growth medium alone. The RD peak potential of the hydrophilic MHDA surface remained, further largely unaffected but the RD peak of the hydrophobic MHD SAM is distinctly shifted compared to the MHD SAM alone. The shifts were further in different directions for the S. mutans biofilm...

  19. 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.


    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.

  20. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry (United States)

    Sundararaman, Ravishankar; Goddard, William A.; Arias, Tomas A.


    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.

  1. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry. (United States)

    Sundararaman, Ravishankar; Goddard, William A; Arias, Tomas A


    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.

  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


    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

  3. Etude des propriétés magnéto-optiques des couches minces à base ...

    African Journals Online (AJOL)

    Etude des propriétés magnéto-optiques des couches minces à base de ferrite de cobalt obtenues par voie sol-gel. ... Les courbes obtenues à la longueur d'onde de 820 nm présentent des cycles d'hystérésis avec des rotations rémanentes de 40, 60 et 81°/cm. Ces résultats présentent une excellente rotation Faraday de ...

  4. Etudes physiques des mélanges eau-cryoprotecteurs (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

  5. 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


    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

  6. Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 (M = Mn, Fe). (United States)

    Laha, S; Natarajan, S; Gopalakrishnan, J; Morán, E; Sáez-Puche, R; Alario-Franco, M Á; Dos Santos-Garcia, A J; Pérez-Flores, J C; Kuhn, A; García-Alvarado, F


    We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to

  7. 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.


    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

  8. 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.


    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

  9. Etude vibroacoustique d'un systeme coque-plancher-cavite avec application a un fuselage simplifie (United States)

    Missaoui, Jemai

    L'objectif de ce travail est de developper des modeles semi-analytiques pour etudier le comportement structural, acoustique et vibro-acoustique d'un systeme coque-plancher-cavite. La connection entre la coque et le plancher est assuree en utilisant le concept de rigidite artificielle. Ce concept de modelisation flexible facilite le choix des fonctions de decomposition du mouvement de chaque sous-structure. Les resultats issus de cette etude vont permettre la comprehension des phenomenes physiques de base rencontres dans une structure d'avion. Une approche integro-modale est developpee pour calculer les caracteristiques modales acoustiques. Elle utilise une discretisation de la cavite irreguliere en sous-cavites acoustiques dont les bases de developpement sont connues a priori. Cette approche, a caractere physique, presente l'avantage d'etre efficace et precise. La validite de celle-ci a ete demontree en utilisant des resultats disponibles dans la litterature. Un modele vibro-acoustique est developpe dans un but d'analyser et de comprendre les effets structuraux et acoustiques du plancher dans la configuration. La validite des resultats, en termes de resonance et de fonction de transfert, est verifiee a l'aide des mesures experimentales realisees au laboratoire.

  10. 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


    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)

  11. 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


    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)

  12. Covalent dimers of 1,3-diphenylisobenzofuran for singlet fission: synthesis and electrochemistry. (United States)

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


    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.

  13. 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.


    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.

  14. Etude des etats electroniques en champ magnetique dans le niveau de Landau N=0 de la tricouche ABC de graphene (United States)

    Rondeau, Maxime

    Dans cet ouvrage nous etudions les phases du gaz d'electrons bidimensionnel dans la tricouche de graphene en empilement ABC. En partant du modele des liaisons fortes et en faisant l'approximation du continuum autour des vallees K +, K-, nous obtenons un modele effectif a deux bandes qui permet de decrire la physique de basse energie des electrons en champ magnetique dans cette structure. Ce modele contient trois orbitales degenerees dans le niveau de Landau N = O. Ce dernier est donc 12N φ, fois degeneres en incluant les degres de liberte de spin et de vallee. En ajoutant l'interaction de Coulomb au systeme et en considerant seulement les remplissages v = -5, -4, -4, 5 afin d'avoir un systeme a trois niveaux, nous etudions le diagramme de phase du gaz d'electrons en fonction d'un biais electrique entre les couches externes. Nous trouvons une phase d'onde de densite de charge bidimensionnelle (ODC2D) comme etat fondamental du systeme. Cette ODC2D se nomme cristal dans ce memoire et nous derivons ses proprietes de transports et ses modes collectifs. Nous discutons egalement du caractere topologique de ce cristal. Notre etude englobe aussi les phases liquides avec ou sans coherence orbitale. Nous concluons notre memoire par l'etude de quelques signatures experimentales des phases du gaz d'electrons dans la tricouche.

  15. How to Develop Electrochemistry SETS-Based Interactive E-Book? (United States)

    Munawwarah, M.; Anwar, S.; Sunarya, Y.


    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.

  16. Photophysics and electrochemistry relevant to photocatalytic water splitting involved at solid–electrolyte interfaces

    KAUST Repository

    Shinagawa, Tatsuya


    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.

  17. Boosted electrochemistry properties of Cu4[(OH)0.29Cl0.71](OH)6 hexagonal prisms by 3D-cage atomic configuration of (100) facet (United States)

    Zhang, An; Teng, Fei; Zhang, Qiqi; Zhai, Yifei; Liu, Zailun; Liu, Zhe; Gu, Wenhao; Hao, Weiyi; Abideen, Zain Ul; Teng, Yiran


    The Cu4[(OH)0.29Cl0.71](OH)6 hexagonal prisms, nanoplates and nanosheets are prepared by a simple hydrothermal method, and we have mainly investigated their electrochemistry properties. At 31.25, 62.5, 125, 250 and 500 mAg-1, the discharge capacitances of hexagonal prisms (S0) electrode are 1186, 1023, 969, 934 and 918 mFg-1, respectively; whereas 547, 508, 469, 438 and 375 mFg-1 for hexagonal nanosheets (S10), respectively. The capacitance of 3-8 μm-long hexagonal prisms (0.25 m2g-1) is 2 times higher than that of 50-100 nm-thick hexagonal nanosheets (3.54 m2g-1), which is obviously beyond our imagination. The high capacitance of the former sample has been mainly attributed to the atom configuration of {100} facets and the high electrical conductivity. Compared with the hexagonal tunnel atom configuration of {001} facets, the three-dimensional (3D) cage atom configuration in {100} facets favors for the charge storage, thus leading to a higher capacitance of hexagonal prisms, which has rarely been reported yet. Further, the hexagonal prisms have a higher electrical conductivity than nanoplates and nanosheets, suggesting that the one-dimensional (1D) microstructure is beneficial to the electron transfer. This work enlightens us that the electrochemistry properties of materials can be improved by the exposed facets with unique atom configuration.

  18. Effect of Concentration on the Electrochemistry and Speciation of the Magnesium Aluminum Chloride Complex Electrolyte Solution. (United States)

    See, Kimberly A; Liu, Yao-Min; Ha, Yeyoung; Barile, Christopher J; Gewirth, Andrew A


    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

  19. Electrochemistry of Centered Hexanuclear Zirconium Halide Clusters in Ambient-Temperature Chloroaluminate Molten Salts. (United States)

    Sun, Dong; Hughbanks, Timothy


    Ambient temperature AlCl(3)-1-ethyl-3-methylimidazolium chloride (ImCl) molten salts, both basic (40/60 mol % AlCl(3)/ImCl) and acidic (60/40 mol % AlCl(3)/ImCl), were used in an electrochemical investigation of centered hexanuclear zirconium halide clusters. In the basic molten salt, these [(Zr(6)ZCl(12))Cl(6)](n-) (Z = Be, B, C, Mn, Fe) centered clusters exhibit the following electrochemical reactions on a glassy carbon electrode (potentials vs Al/Al(3+)): [(Zr(6)BeCl(12))Cl(6)](n)()(-) + e(-) right harpoon over left harpoon [(Zr(6)BeCl(12))Cl(6)](()(n)()(+1))(-), E(1/2) = -0.613 V (n = 4), E(1/2) = -1.085 V (n = 5); [(Zr(6)BCl(12))Cl(6)](n)()(-) + e(-) right harpoon over left harpoon [(Zr(6)BCl(12))Cl(6)](()(n)()(+1))(-), E(1/2) = -0.365 V (n = 4), E(1/2) = 0.072 V (n = 3); [(Zr(6)CCl(12))Cl(6)](n)()(-) + e(-) right harpoon over left harpoon [(Zr(6)CCl(12))Cl(6)](()(n)()(+1))(-), E(1/2) = 0.230 V (n = 3); [(Zr(6)MnCl(12))Cl(6)](4)(-) + e(-) right harpoon over left harpoon [(Zr(6)MnCl(12))Cl(6)](5)(-), E(1/2) = -0.432 V. In the acidic melt, only electrochemical reactions [(Zr(6)BeCl(12))(AlCl(4))(6)](n)()(-) + e(-) right harpoon over left harpoon [(Zr(6)BeCl(12))(AlCl(4))(6)](()(n)()(+1))(-), E(1/2) = -0.069 V (n = 5), E(1/2) = 0.504 V (n = 4), and [(Zr(6)BCl(12))(AlCl(4))(6)](4)(-) + e(-) right harpoon over left harpoon [(Zr(6)BCl(12))(AlCl(4))(6)](5)(-), E(1/2) = 0.700 V are clearly observed. These data is consistent with less systematic observations of oxidation of these clusters in solution. No unambiguous one-electron electrochemical reduction nor oxidation is observable for the Fe-centered cluster in the ionic liquids. The half-wave potentials of the above reactions of the Be-, B-, C-, and Mn-centered clusters are controlled largely by clusters' charges. This correlation of redox potentials allows a useful direct comparison with data for related hexanuclear niobium clusters in the literature.

  20. 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


    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

  1. 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


    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)

  2. 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


    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

  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


    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. Etude theorique et experimentale des evaporateurs de dioxyde de carbone operant dans des conditions de givrage (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

  5. Contribution to the theoretical and experimental study of the electron-volt effect in N-P junctions; Contribution a l'etude theorique et experimentale de l'effet electronvoltaique dans les jonctions N-P

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Van, Dong [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires


    , taking into account other phenomena which occur at low temperature. In the fourth part, results concerning the healing of the defects and protection measures against too energetic {beta} rays are described. A healing difference was observed between the lifetime and the conductivity. Finally, interesting results were obtained from experiments using a cadmium sulphide film to transform the {beta} particles of {sup 90}Sr-{sup 90}Y into photons. (author) [French] Le but propose dons le cadre de ce travail est d'etudier le comportement d'une jonction semi-conductrice sous l'action des rayons {beta}. L'etude a porte d'une part sur la conversion directe de l'energie rayonnee par une source radioactive en energie electrique utilisable a l'aide des jonctions N-P, et d'autre part sur la cinetique des defauts produits dans les cristaux de semi-conducteur par les rayons {beta} de grande energie. Dans la premiere partie du travail, on a essaye de completer les theories anterieures de l'effet electron-voltaique dans les jonctions en faisant une analyse mathematique de l'effet. Ceci a permis d'atteindre une equation unique dans laquelle figurent les parametres electriques et geometriques du semi-conducteur, de la jonction et les proprietes du rayonnement incident. D'autre part, on a etudie d'une maniere plus approfondie le courant de diffusion des porteurs de charge crees par le bombardement en tenant compte de tous les facteurs intervenant dans l'expression de l'efficacite de collection de charge d'une jonction. Dans la deuxieme partie, ou des experiences d'irradiation des jonctions N-P ont ete effectuees avec une source de {sup 90}Sr- {sup 90}Y, on a signale l'interet particulier d'une jonction d'arseniure de gallium susceptible de travailler a des temperatures relativement elevees (voisines de 100 deg. C). La troisieme partie presente l'etude des defauts crees dans un cristal de

  6. Directed homology

    DEFF Research Database (Denmark)

    Fahrenberg, Uli


    We introduce a new notion of directed homology for semicubical sets. We show that it respects directed homotopy and is functorial, and that it appears to enjoy some good algebraic properties. Our work has applications to higher-dimensional automata.......We introduce a new notion of directed homology for semicubical sets. We show that it respects directed homotopy and is functorial, and that it appears to enjoy some good algebraic properties. Our work has applications to higher-dimensional automata....

  7. The study of neutron transport by oscillation method; Etude du transport des neutrons par la methode de modulation

    Energy Technology Data Exchange (ETDEWEB)

    Raievski, V


    The oscillation method is of very general use for studying the behavior of thermal neutrons in media. The main experiments are described and a general theory of them is given. This theory, which is presented in the first part, is established using the two-group approximation which has proved its efficiency in the case of thermal neutron piles. The validity of the two-group approximation is recalled. This allows definition of the meaning of the parameters used in the theory and which are measured in these experiments. The experiments carried out by this method are described, especially those performed at the Centre d'Etudes Nucleaires de Saclay where the method has been extensively used. These experiments are interpreted by means of the general theory given previously. In this way, the identity of parameters measured by this method and those given by the theory is proved. This is particularly conclusive is the case of the mean life of neutrons in a pile. (author) [French] La methode de modulation est un procede tres general d'etude des proprietes neutroniques des milieux contenant des neutrons thermiques. Le present rapport a pour but de decrire les principales de ces experiences et d'en donner une theorie generale. Cette theorie, exposee dans la premiere partie, est etablie dons le cadre de l'approximation a deux groupes de vitesse qui a prouve son efficacite dons le cas des piles a neutrons thermiques. Le domaine de validite de l'approximation a deux groupes est rappele au debut, ce qui permet de definir avec precision la signification des parametres qui entrent dons la theorie et qui font l'objet de ces mesures. La deuxieme partie decrit les experiences realisees, en particulier celles effectuees au Centre d'Etudes Nucleaires de Saclay ou la methode a ete considerablement developpee. Ces experiences sont interpretees dans le cadre de la theorie generale exposee precedemment. On prouve ainsi l'identite des parametres mesures

  8. Randomized control trial for the assessment of the anti-albuminuric effects of topiroxostat in hyperuricemic patients with diabetic nephropathy (the ETUDE study). (United States)

    Kato, Sawako; Ando, Masahiko; Mizukoshi, Toshihiro; Nagata, Takanobu; Katsuno, Takayuki; Kosugi, Tomoki; Tsuboi, Naotake; Maruyama, Shoichi


    Proteinuria is an established risk factor for diabetic nephropathy. Recent studies indicate that some xanthine oxidase inhibitors have a renoprotective effect. The aim of this study was to assess whether topiroxostat reduces albuminuria in hyperuricemic patients with diabetic nephropathy and overt proteinuria. The ETUDE study is an ongoing 24-week, multicenter, open-label, randomized (1:1), parallel group study involving hyperuricemic patients with diabetic nephropathy (estimated glomerular filtration rate [eGFR] ≥ 20 mL/min/1.73 m(2)) and overt proteinuria (0.3 ≤ urine protein to creatinine ratio (UPCR) ETUDE trial is the first randomized controlled study of topiroxostat in hyperuricemic patients with diabetic nephropathy and overt proteinuria. We will clarify the pleiotropic function of topiroxostat including an anti-albumiuric effect as well as its effects on safely decreasing serum uric acid levels.

  9. Point-of-care ultrasonography adoption in Canada: using diffusion theory and the Evaluation Tool for Ultrasound skills Development and Education (ETUDE). (United States)

    Woo, Michael Y; Frank, Jason R; Lee, A Curtis


    Point-of-care ultrasonography (PoCUS) first appeared in the 1980s in North America, but the extent of the diffusion of its adoption is unknown. We characterized early PoCUS adoption by emergency physicians in Canada and its barriers to use using Rogers' diffusion of innovations theory. We developed a questionnaire based on a pilot study and literature review to assess past, current, and potential use of PoCUS and potential barriers to adoption. A Dillman technique for electronic surveys was used for dissemination. Using Rogers' diffusion of innovations theory, we developed and validated the Evaluation Tool for Ultrasound skills Development and Education (ETUDE). ETUDE scores allowed categorization of respondents into innovators, early adopters, majority, and nonadopters. Descriptive statistics, correlations, and χ² statistics were used to analyze the data. The 296 respondents (36.4% of 814 surveyed) had a median age of 40 and were 72.5% male. Adoption scores using ETUDE revealed nonadopters (18.8%), majority (28.7%), early adopters (34.5%), and innovators (18.0%). Respondents endorsed "always" using PoCUS currently and in the future for focused assessment with sonography in trauma (FAST) (current 41.8%/future 88.4%), first trimester pregnancy (current 23.3%/future 73.7%), suspected abdominal aortic aneurysm (current 32.7%/future 92.6%), basic cardiac indications (current 30.7%/future 87.5%), and central venous catheterization (current 17.0%/future 80.3%). Several barriers to PoCUS were identified for part-time emergency physicians and those working in inner-city/urban/suburban settings. This is the first study to determine the state of adoption and barriers to the introduction of PoCUS in Canadian emergency medicine practice. The novel validated ETUDE instrument should be used to evaluate the uptake of PoCUS over time.

  10. Etude de la transition ferroelectrique-ferroelastique du KD2PO4 forme du front de phase en fonction du gradient thermique


    Kvítek, Zdeněk


    Etude de la transition ferroelectrique-ferroelastique du KD2PO4 forme du front de phase en fonction du gradient thermique The thesis explores complex process of first order transition of KD2PO4 crystal from tetragonal phase to ferroelectric - ferroelastic orthorhombic phase and back at temperature 209 K. The experimental set up of nitrogeneous cryostat allowes temperature and temperature gradient variations during simultaneous three axes optical sample observations, dielectric measurements. T...

  11. The development of a very high stability electrostatic generator (1962); Etude et realisation d'un generateur electrostatique a tres haute stabilite (1962)

    Energy Technology Data Exchange (ETDEWEB)

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


    This thesis deals with the study of an electrostatic high voltage generator having a voltage stability of the order of 10{sup -6} per minute. This equipment should be very useful in electron microscopy. The electrostatic generator is studied as a control system element: transfer function, parasitic signals and noise are determined and a mathematical model is proposed. A theoretical study of the open loop transfer function, stability, transient response, voltage stabilization of five different control systems shows which one should be able to fulfill the requirements There follows a detailed study of drift, a description of the actual system and performance data. (author) [French] Cette etude concerne un generateur electrostatique capable de fournir une tres haute tension continue dont la stabilite relative est de l'ordre de 10{sup -6} pendant une minute. Une telle performance rend cet appareillage tres utile en microscopie electronique. La generatrice electrostatique est etudiee en tant qu'element d'un systeme asservi: on determine successivement la fonction de transfert, les perturbations, le bruit de fond et le modele mathematique. L'etude de cinq differents circuits de regulation en ce qui concerne leur fonction de transfert, stabilite, reponse en regime transitoire, attenuation des perturbations, permettra de choisir le systeme qui semble le mieux repondre aux exigences. Viennent ensuite une etude detaillee de la derive, la description de la realisation pratique et les resultats de mesure. (auteur)

  12. Peter Debye and Electrochemistry

    Indian Academy of Sciences (India)

    Keywords. Debye–Hückel theory; electrolytic conductivity; activity co-efficient; transport properties. Author Affiliations. A K Shukla1 T Prem Kumar2. Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India. Electrochemical Power Systems Division Central Electrochemical Research ...

  13. Peter Debye and Electrochemistry

    Indian Academy of Sciences (India)

    The most frequent exam question related to activity coefficients… .” The importance and ... physics, mathematics and electrical engineering. His entry into chemistry was rather late, but he was a dominant figure in physical chemistry and chemical physics during the first half of the 20th century. Debye, along with Erich Hückel, ...

  14. Theoretical Chemistry and Electrochemistry

    Indian Academy of Sciences (India)


    Faradaic rectification; (ii) effect of diffuse double layer on electrode kinetics; (iii) accel- erated Tafel plots for measuring rates of corrosion; (iv) estimation of the activity coeffi- cients for mixed electrolytes, beyond the Debye–Huckel theory and (v) novel identities for a class of special functions of mathematical physics.

  15. Peter Debye and Electrochemistry

    Indian Academy of Sciences (India)

    Debye won the 1936 Nobel Prize in Chemistry for his contri- butions to molecular structure, dipole moment relationship and for diffraction of X-rays and electrons. Electrochemists, however, remember him for the Debye–Hückel limiting law that describes the behavior of strong electrolytes. In explain- ing the non-ideal ...

  16. Electrochemistry for Energy Conversion (United States)

    O'Hayre, Ryan


    Imagine a laptop computer that runs for 30 hours on a single charge. Imagine a world where you plug your house into your car and power lines are a distant memory. These dreams motivate today's fuel cell research. While some dreams (like powering your home with your fuel cell car) may be distant, others (like a 30-hour fuel cell laptop) may be closer than you think. If you are curious about fuel cells---how they work, when you might start seeing them in your daily life--- this talk is for you. Learn about the state-of-the art in fuel cells, and where the technology is likely to be headed in the next 20 years. You'll also be treated to several ``behind-the scenes'' glimpses of cutting-edge research projects under development in the Renewable Energy Materials Center at the Colorado School of Mines--- projects like an ``ionic transistor'' that works with protons instead of electrons, and a special ceramic membrane material that enables the ``uphill'' diffusion of steam. Associate Professor Ryan O'Hayre's laboratory at the Colorado School of Mines develops new materials and devices to enable alternative energy technologies including fuel cells and solar cells. Prof. O'Hayre and his students collaborate with the Colorado Fuel Cell Center, the Colorado Center for Advanced Ceramics, the Renewable Energy Materials Science and Engineering Center, and the National Renewable Energy Laboratory.[4pt] In collaboration with Ann Deml, Jianhua Tong, Svitlana Pylypenko, Archana Subramaniyan, Micahael Sanders, Jason Fish, Annette Bunge, Colorado School of Mines.

  17. Magnetic effects in electrochemistry

    Directory of Open Access Journals (Sweden)



    Full Text Available The effect of imposed magnetic fields onto the electrodeposition of magnetic (nickel and non – magnetic (copper metals was analysed. Also, magnetic properties of electrochemically obtained nanocontacts were examined. An effort to establish a possible correlation between the morphologies of the nanocontacts and the effect of the very large ballistic magnetoresistance (BMR effect was made.


    African Journals Online (AJOL)


    FERRICENIUM REDOX COUPLE AT GLASSY CARBON. ELECTRODE. N. S. Neghmouche, A. Khelef and T. Lanez*. Institute of sciences and technology, University Centre of El-Oued, B.P.789, 39000,. El-Oued, Algeria. Received: 25 ...

  19. 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.


    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.

  20. Depth probing of the hydride formation process in thin Pd films by combined electrochemistry and fiber optics-based in situ UV/vis spectroscopy. (United States)

    Wickman, Björn; Fredriksson, Mattias; Feng, Ligang; Lindahl, Niklas; Hagberg, Johan; Langhammer, Christoph


    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.

  1. End-of-Discharge and End-of-Life Prediction in Lithium-Ion Batteries with Electrochemistry-Based Aging Models (United States)

    Daigle, Matthew; Kulkarni, Chetan S.


    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.

  2. Study of radio-active ions in the atmosphere; Etude des ions radioactifs de l'atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Renoux, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires


    A comparative study is made of active, deposits of radon and thoron in suspension in the atmosphere by means of {alpha} radiation counting, using ZELENY tubes, scattering equipment, filter papers or membranes. It has been possible to show the existence of small and large ions which are negative and positive, as well as of neutral radio-active nuclei; their properties are studied. A theoretical interpretation of the results is presented. The average content of radon (using the Ra A concentration) and of Th B in the air has been determined. The radioactive equilibrium between radon and its daughter products in atmospheric air are examined. The techniques developed for active radon and thoron deposits are applied to the study of artificial radio-activity, the analyses being carried out by means of {gamma} spectrometry. (author) [French] On effectue une etude comparative entre les depots actifs du radon et du thoron en suspension dont l'atmosphere a l'aide de comptages de rayonnement {alpha}, en utilisant des tubes de ZELENY, une batterie de diffusion, des papiers filtres ou des membranes. On met ainsi en evidence la presence de petits et gros ions negatifs et positifs, ainsi que celle de noyaux neutres radioactifs, et on etudie leurs proprietes. Une Interpretation theorique des resultats obtenus est developpee. On determine la teneur moyenne de l'air en radon (a partir de la concentration en Ra A) et en Th B. L'equilibre radioactif entre le radon et ses descendants, dans l'air atmospherique, est examine. Les Techniques mises au point pour les depots actifs du radon et du thoron sont appliquees a l'etude de la radioactivite artificielle, les depouillements s'effectuant par spectrometrie {gamma}. (auteur)

  3. Study of thermocouples for control of high temperatures; Etude de thermocouples pour le reperage des hautes temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Villamayor, M. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Faculte des Sciences de l' Universite de Lyon - 69 (France)


    Previous works have shown that the tungsten-rhenium alloys thermocouples were a good instrument for control of high temperatures. From its, the author has studied the W/W 26 per cent and W 5 per cent Re/W 26 per cent Re french manufactured thermocouples and intended for control of temperatures in nuclear reactors until 2300 deg. C. In 'out-pile' study he determines the general characteristics of these thermocouples: average calibration curves, thermal shocks influence, response times, and alloys allowing the cold source compensation. The evolution of these thermocouples under thermal neutron flux has been determined by 'in-pile' study. The observations have led the author to propose a new type of thermocouples settled of molybdenum-columbium alloys. (author) [French] Des travaux anterieurs ont montre que les thermocouples des alliages tungstene-rhenium etaient susceptibles de reperer avec precision des hautes temperatures. A partir de la, l'auteur a etudie las thermocouples W/W 26 pour cent Re et W 5 pour cent Re/W 26 pour cent Re de fabrication francaise et destines au controle des temperatures dans les reacteurs nucleaires, jusqu'a 2300 deg. C Dans l'etude 'hors-pile' il a determine les caracteristiques generales de ces thermocouples: courbes d'etalonnage moyen, influence des chocs thermiques, temps de reponse, et alliages assurant la compensation de soudure froide. L'etude 'en-pile' a permis de rendre compte de l'evolution de ces thermocouples sous flux neutroniques. Les phenomenes observes ont conduit l'auteur a proposer un nouveau type de thermocouples constitues d'alliages molybdene-niobium. (auteur)

  4. Direct Democracy

    DEFF Research Database (Denmark)

    Beramendi, Virginia; Ellis, Andrew; Kaufman, Bruno

    of direct democracy mechanisms in specific contexts. These country case studies allow for in depth discussion of particular issues, including signature collection and voter participation, campaign financing, media coverage, national variations in the usage of direct democracy procedures and national lessons...

  5. Advance Directives (United States)

    ... Types Bladder Cancer Breast Cancer Colorectal Cancer Kidney (Renal Cell) Cancer Leukemia Liver Cancer Lung Cancer Lymphoma ... about advance directives. Two well-known ones are: Aging With Dignity Aging with Dignity is a national ...

  6. Directing Creativity

    DEFF Research Database (Denmark)

    Darsø, Lotte; Ibbotson, Piers


    . 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......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...... 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....

  7. Direct Heat

    Energy Technology Data Exchange (ETDEWEB)

    Lienau, P.J.


    Potential resources and applications of earth heat in the form of geothermal energy are large. United States direct uses amount to 2,100 MWt thermal and worldwide 8,850 MWt above a reference temperature of 35 degrees Celsius. Space and district heating are the major direct uses of geothermal energy. Equipment employed in direct use projects is of standard manufacture and includes downhole and circulation pumps, transmission and distribution pipelines, heat exchangers and convectors, heat pumps and chillers. Direct uses of earth heat discussed are space and district heating, greenhouse heating and fish farming, process and industrial applications. The economic feasibility of direct use projects is governed by site specific factors such as location of user and resource, resource quality, system load factor and load density, as well as financing. Examples are presented of district heating in Klamath Falls, and Elko. Further developments of direct uses of geothermal energy will depend on matching user needs to the resource, and improving load factors and load density.

  8. Purines bearing phenanthroline or bipyridine ligands and their Ru II complexes in position 8 as model compounds for electrochemical DNA labeling - synthesis, crystal structure, electrochemistry, quantum calculations, cytostatic and antiviral activity

    Czech Academy of Sciences Publication Activity Database

    Vrábel, Milan; Hocek, Michal; Havran, Luděk; Fojta, Miroslav; Votruba, Ivan; Klepetářová, Blanka; Pohl, Radek; Rulíšek, Lubomír; Zendlová, Lucie; Hobza, Pavel; Shih, I.; Mabery, E.; Mackman, R.

    -, č. 12 (2007), s. 1752-1769 ISSN 1434-1948 R&D Projects: GA ČR GA203/05/0043; GA ČR(CZ) GD203/05/H001; GA MŠk LC512; GA MŠk(CZ) LC06035 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z50040507 Keywords : purines * Ru complexes * electrochemistry Subject RIV: CC - Organic Chemistry Impact factor: 2.597, year: 2007

  9. Etude thermo-hydraulique de l'ecoulement du moderateur dans le reacteur CANDU-6 (United States)

    Mehdi Zadeh, Foad

    importante, se traduisant par l'accroissement de la puissance du reacteur. Ceci peut avoir des consequences majeures pour la surete nucleaire. Une modelisation CFD (Computational Fluid Dynamics) detaillee tenant compte des effets locaux s'avere donc necessaire. Le but de ce travail de recherche est de modeliser le comportement complexe de l'ecoulement du moderateur au sein de la cuve d'un reacteur nucleaire CANDU-6, notamment a proximite des tubes de calandre. Ces simulations servent a identifier les configurations possibles de l'ecoulement dans la calandre. Cette etude consiste ainsi a formuler des bases theoriques a l'origine des instabilites macroscopiques du moderateur, c.-a-d. des mouvements asymetriques qui peuvent provoquer l'ebullition du moderateur. Le defi du projet est de determiner l'impact de ces configurations de l'ecoulement sur la reactivite du reacteur CANDU-6.

  10. La structure de l'eau liquide: Une etude thermique par spectroscopie infrarouge (United States)

    Larouche, Pascal

    Le probleme de la structure de l'eau liquide est important car l'eau est le liquide le plus present sur Terre, et complexe, la quete d'un modele precis pour decrire comment fonctionne ce liquide ayant debute des la fin du dix-neuvieme siecle. Cette etude aborde ce probleme en etudiant l'effet de l'augmentation de la temperature sur H2O et D 2O purs a l'aide de la spectroscopie infrarouge. L'intervalle de temperatures scrute est 29--93.1°C. Les spectres enregistres sont des spectres MIR-ATR entre 650 et 6000 cm-1 . L'analyse par facteurs de ces donnees permet de montrer que deux et seulement deux facteurs principaux sont necessaires pour decomposer tous les spectres experimentaux. Ces resultats sont confirmes grace a l'analyse par facteurs de spectres de la region FIR. Par la suite, la transformation en spectres de la partie reelle n et imaginaire k de l'indice de refraction permet de combiner les donnees des regions MIR et FIR. Une fois ce calcul termine, les spectres de transmission complets de H 2O et D2O entre 25 et 90°C sont connus. Ils sont ensuite utilises pour calculer par extrapolation le spectre des especes constituant l'eau liquide, puis leur abondance en fonction de la temperature. L'extrapolation de ces abondances montre que les especes correspondent a des temperatures limites de --18 et 122°C. Par la suite, la decomposition gaussienne des spectres d'especes met en evidence la riche structure de ces objets et permet de demontrer que l'apparent deplacement du massif d'absorption OH (OD) est produit par une variation de l'intensite des bandes et non pas de leur deplacement. L'examen attentif des spectres des especes prouve qu'il n'y a pas de OH libres crees par l'augmentation de la temperature: meme a 93.1°C, chaque molecule possede quatre liens-H. Ces conclusions sont de plus confirmees par une analyse thermodynamique du passage des molecules de la phase solide a la phase gazeuse. Pour diversifier la nature des resultats experimentaux utilises, des

  11. Study of the artificial radioactivity of the marine medium using gamma spectrometry (1962-1966); Etude de la radioactivite artificielle du milieu marin par spectrometrie gamma (1962-1966)

    Energy Technology Data Exchange (ETDEWEB)

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


    The results described in this study are relative to the artificial radioactivity of such elements as zirconium-95, niobium-95, ruthenium-103, ruthenium-106, cerium-141, cerium-144 and praseodymium-144 which were present in the atmospheric fallout between 1962 and 1964, and their incidence in superficial marine waters. Various physical, chemical or biological processes are studied by a high sensitivity gamma ray spectrometry technic, using those radioelements as 'tracers'. The change of state in sea water of an important fraction (about 50 per cent) of the radioactive particles going into the soluble phase - this phenomenon was not expected for those radioelements - controls the processes of accumulation in the planktonic biomass and the diffusion towards deeper waters. On the other hand, an 'in situ' spectrometry method is described. It enables the direct measurement in the sea of very low concentrations of some gamma ray emitters. The application of this method has made possible to carry out numerous observations in the surface waters of the Western Mediterranean sea and in the Bay of Biscay. It is shown that the mixing depth is closely connected to the depth of the thermocline. An accumulation process at this level is observed. The diffusion coefficients are similar to the thermal turbulent coefficient. The existence during several months of 'compartments' is established for the surface waters of the Bay of Biscay. From the establishment of the budget of fall-out, a comparative study shows that the rate of radioactive fallout on the maritime zone considered is always two to three times higher than on the neighbouring continental regions. Several explanations of this phenomenon are discussed. (author) [French] Les resultats decrits dans cette etude concernent la radioactivite artificielle sous forme de zirconium-95, niobium-95, ruthenium-103, ruthenium-106, cerium-141, cerium-144 et praseodyme-144 apportee par la retombee

  12. Direct marketing

    Directory of Open Access Journals (Sweden)

    Čičić Muris


    Full Text Available Direct Marketing (DM is usually treated as unworthy activity, with actions at the edge of legality and activities minded cheating. Despite obvious problems regarding ethics and privacy threat, DM with its size, importance and role in a concept of integrated marketing communication deserves respect and sufficient analysis and review

  13. Electrochemistry-mass spectrometry for in-vitro determination of selected chemotherapeutics and their electrochemical products in comparison to in-vivo approach. (United States)

    Szultka-Mlynska, Malgorzata; Buszewski, Boguslaw


    Chemotherapeutics are among the most frequently prescribed medications in modern medicine. They are widely prescribed; however, problems with organisms developing resistance to these drugs means that their efficacy may be lost, so care should be taken to avoid unnecessary prescription. It is therefore of great interest to study the detailed metabolism of these biologically active compounds. This study aimed at developing an efficient analytical protocol for the determination of in-vitro electrochemical products of selected antibiotic drugs (amoxicillin, cefotaxime, fluconazole, linezolid, metronidazole and moxifloxacin). Combination of electrochemistry (EC) and mass spectrometry (MS) was applied for the in-vitro determination of the studied antibiotics and their electrochemical products. To identify the structure of the detected electrochemical products, MS/MS experiments were performed. This was one of the first applications of the EC system for generation of electrochemical products produced from antibiotic drugs. Adjustment of appropriate conditions and such parameters as the potential value, mobile phase (pH), working electrode and temperature had significant influence on electrochemical simulations and the creation of selected derivatives. Consequently, several working electrodes were evaluated for this purpose. In most of the studied cases, mainly two types of products were observed. One corresponded to an increase in mass by 14Da, which can be explained by a process consisting of oxidation (+16 m/z) and dehydrogenation (-2 m/z); The second in turn showed mass reduction by 14Da, which can be attributed to the loss of -CH2 as a result of N-demethylation. The performed experiments consisted of two stages: electrochemical oxidation of the analyzed samples (phase I of metabolic transformation), and addition of glutathione (GSH) for follow-up reactions (phase II conjunction). The electrochemical results were compared to in-vivo experiments by analyzing urine

  14. Direct ELISA. (United States)

    Lin, Alice V


    First described by Engvall and Perlmann, the enzyme-linked immunosorbent assay (ELISA) is a rapid and sensitive method for detection and quantitation of an antigen using an enzyme-labeled antibody. Besides routine laboratory usage, ELISA has been utilized in medical field and food industry as diagnostic and quality control tools. Traditionally performed in 96-well or 384-well polystyrene plates, the technology has expanded to other platforms with increase in automation. Depending on the antigen epitope and availability of specific antibody, there are variations in ELISA setup. The four basic formats are direct, indirect, sandwich, and competitive ELISAs. Direct ELISA is the simplest format requiring an antigen and an enzyme-conjugated antibody specific to the antigen. This chapter describes the individual steps for detection of a plate-bound antigen using a horseradish peroxidase (HRP)-conjugated antibody and luminol-based enhanced chemiluminescence (ECL) substrate. The methodological approach to optimize the assay by chessboard titration is also provided.

  15. Studies of light water lattices by the homogeneous boron poisoning technique; Etude des reseaux a eau legere par la methode d'empoisonnement homogene au bore

    Energy Technology Data Exchange (ETDEWEB)

    Bailly, J.; Calament, J.; Girard, Y.; Golinelli, C. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires


    By homogeneously poisoning a critical facility with boric acid, one can balance important reactivities. Furthermore this technique is particularly interesting, due to the fact that it allows the substitution of cross sections to kinetic parameters in lattice calculations. With this use of boric acid as a poison arise important technological problems which are described in this report, the last part of which deals with the accuracy of the measurements made in these conditions. The main features of a lattice study made according to this moderator poisoning technique concern the determination of the concentration of dissolved boron which makes the multiplying assembly just critical and the determination of the reactivity factor as a function of temperature (this study has been carried out fill above 95 deg. C). (authors) [French] L'empoisonnement homogene d'une facilite critique par l'acide borique permet, outre d'effectuer des compensations de reactivites importantes, de jouer le role d'un intermediaire de mesure particulierement interessant par le fait qu'il conduit a substituer, dans le calcul des reseaux, des sections efficaces aux parametres cinetiques. Cette utilisation de l'acide borique comme poison ne va pas sans poser d'importants problemes technologiques qui sont decrits dans la presente etude, dont la derniere partie est consacree a la precision de mesures effectuees dans, ces conditions. Les points essentiels de l'etude d'un reseau suivant cette technique d'empoisonnement du moderateur, concernant la mesure de la concentration de bore dissous qui rend l'assemblage multiplicateur juste critique, ainsi que la determination du coefficient de reactivite en fonction de la temperature (l'etude a ete poussee au-dela de 95 deg. C). (auteurs)

  16. Study of cerenkov radiation. Production of {gamma} rays by electron accelerators; Etude du rayonnement de freinage. Production de rayons {gamma} par des accelerateurs d'electrons

    Energy Technology Data Exchange (ETDEWEB)

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


    This study is a critical comparison of the theories of Bremsstrahlung. Experimental results obtained by the production of {gamma} radiation with electron accelerators are compared to the theoretical results in order to estimate the extent to which the various theories are valid. (author) [French] Cette etude est une synthese des theories du rayonnement de freinage. Des resultats experimentaux, obtenus par la production de rayonnements {gamma} avec des accelerateurs d'electrons, sont compares aux resultats theoriques afin d'evaluer les domaines de validite des diverses theories. (auteur)

  17. Forensic analyses of explosion debris from the January 2, 1992 Pd/D{sub 2}O electrochemistry incident at SRI International

    Energy Technology Data Exchange (ETDEWEB)

    Andresen, B.; Whipple, R.; Vandervoort, D.; Grant, P.


    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. Synthesis, structure, and electrochemistry and magnetic properties of a novel 1D homochiral MnIII(5-Brsalen) coordination polymer with left-handed helical character (United States)

    Dong, Dapeng; Yu, Naisen; Zhao, Haiyan; Liu, Dedi; Liu, Jia; Li, Zhenghua; Liu, Dongping


    A novel homochiral manganese (III) Mn(5-Brsalen) coordination polymer with left-handed helical character by spontaneous resolution on crystallization by using Mn(5-Brsalen) and 4,4-bipyridine, [MnIII(5-Brsalen)(4,4-bipy)]·ClO4·CH3OH (1) (4,4-bipy = 4,4-bipyridine) has been synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analysis and infrared spectroscopy. In compound 1, each manganese(III) anion is six-coordinate octahedral being bonded to four atoms of 5-Brsalen ligand in an equatorial plane and two nitrogen atoms from a 4,4-bipyridine ligand in axial positions. The structure of compound 1 can be described a supramolecular 2D-like structure which was formed by the intermolecular π-stacking interactions between the neighboring chains of the aromatic rings of 4,4-bipyridine and 5-Brsalen molecules. UV-vis absorption spectrum, electrochemistry and magnetic properties of the compound 1 have also been studied.

  19. Surface electrochemistry of CO2 reduction and CO oxidation on Sm-doped CeO(2-x): coupling between Ce(3+) and carbonate adsorbates. (United States)

    Feng, Zhuoluo A; Machala, Michael L; Chueh, William C


    The efficient electro-reduction of CO2 to chemical fuels and the electro-oxidation of hydrocarbons for generating electricity are critical toward a carbon-neutral energy cycle. The simplest reactions involving carbon species in solid-oxide fuel cells and electrolyzer cells are CO oxidation and CO2 reduction, respectively. In catalyzing these reactions, doped ceria exhibits a mixed valence of Ce(3+) and Ce(4+), and has been employed as a highly active and coking-resistant electrode. Here we report an operando investigation of the surface reaction mechanism on a ceria-based electrochemical cell using ambient pressure X-ray photoelectron spectroscopy. We show that the reaction proceeds via a stable carbonate intermediate, the coverage of which is coupled to the surface Ce(3+) concentration. Under CO oxidation polarization, both the carbonate and surface Ce(3+) concentration decrease with overpotential. Under CO2 reduction polarization, on the other hand, the carbonate coverage saturates whereas the surface Ce(3+) concentration increases with overpotential. The evolution of these reaction intermediates was analyzed using a simplified two-electron reaction scheme. We propose that the strong adsorbate-adsorbate interaction explains the coverage-dependent reaction mechanism. These new insights into the surface electrochemistry of ceria shed light on the optimization strategies for better fuel cell electrocatalysts.

  20. Determination of the equilibrium fO2 in bulk samples of H, L, and LL ordinary chondrites by solid-state electrochemistry (United States)

    Osadchii, Valentin O.; Fedkin, Mark V.; Osadchii, Evgeniy G.


    High-temperature solid-state electrochemistry techniques (EMF method) were used to measure the oxygen fugacity (fO2) of the ordinary chondrites Ochansk (H4), Savtschenskoje (LL4), Elenovka (L5), Vengerovo (H5), and Kharkov (L6). The fO2 results are presented in the form of the following equations: logfO2>(Ochansk>)=>(9.39±1.64>)->(3.124∓0.191>)·104·T-1 1070/K(Vengerovo>)=>(6.86±1.73>)->(2.870∓0.196>)·104·T-1 1050/K(Elenovka>)=>(8.37±1.10>)->(3.005∓0.124>)·104·T-1 1050/K(Savtschenskoje>)=>(11.36±0.85>)->(3.289∓0.099>)·104·T-1 1070/K(Kharkov>)=>(7.80±0.44>)->(2.930∓0.050>)·104·T-1 1050/K 1200 K, becomes more reduced than Kharkov (L6) or Elenovka (L5). Measured oxygen fugacity values of meteorites fall within (0.1-1.0)·log fO2 of one another. The possible explanation of discrepancies between measured and calculated values is discussed.

  1. Contribution to the study of the role of diffusion in the growth of crystals from solution; Contribution a l'etude du role de la diffusion dans la croissance des cristaux a partir de solution

    Energy Technology Data Exchange (ETDEWEB)

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


    'un oculaire micrometrique et de chronophotographies. On a d'autre part utilise la methode interferentielle en lumiere polarisee pour determiner la distribution de la concentration au voisinage du cristal; cela a permis, ayant mesure par ailleurs le coefficient de diffusion, de calculer la vitesse de croissance et de constater un desaccord, de l'ordre de deux, avec les mesures directes. Celui-ci peut meme atteindre une valeur de dix dans le cas de substances tres solubles, lesquelles font l'objet d'une etude de R. ITTI. (auteur)

  2. Some aspects of nuclear graphite production in France; Etude generale sur les graphites nucleaires produits en France

    Energy Technology Data Exchange (ETDEWEB)

    Gueron, J.; Hering, H. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Legendre, A. [Pechiney, 75 - Paris (France)


    1) Manufacturing: A summary and results on the CEA-Pechiney purification process are given. Variations in the preparation of green pastes and their effects on graphitized material are described. 2) Physical and mechanical properties: Results are given on: - Statistics of dimensional variatior products having square cross-section. - Statistical variation of thermal expansion coefficients and of electrical conductivity. - Density of normals to carbon layer planes and their connexion with thermal expansion. - Stress-strain cycles and conclusions drawn therefrom. - Mechanical resistance and gas permeability of items for supporting fuel elements. 3) Behaviour under radiation: Alteration under radiation of French graphites irradiated either in G1 pile or in experimental piles, and thermal annealing of those alterations, are given. (author)Fren. [French] 1) Fabrication: On resume le procede d'epuration CEA-PECHINEY, ainsi que diverses modalites de preparation des pates et on expose les resultats obtenus. 2) Proprietes physiques et mecaniques: On indique le resultat d'etudes sur: - la statistique des dimensions de produits a section carree. - celle des variations des coefficients de dilatation thermique et de la conductibilite electrique. - la densite des normales aux plans graphitiques et leur connexion avec la dilatation thermique. - la compression mecanique du graphite. - la solidite mecanique et la permeabilite aux gaz de pieces destinees a supporter des cartouches de combustible. 3) Tenue sous rayonnement: Modification sous rayonnement des graphites fran is irradies soit dans la pile G1, soit dans des piles experimentales, et guerison thermique de ces modifications. (auteur)

  3. Serotonin transporter gene polymorphism and myocardial infarction: Etude Cas-Témoins de l'Infarctus du Myocarde (ECTIM). (United States)

    Fumeron, Frédéric; Betoulle, Dina; Nicaud, Viviane; Evans, Alun; Kee, Frank; Ruidavets, Jean-Bernard; Arveiler, Dominique; Luc, Gérald; Cambien, François


    Depression is a risk factor for myocardial infarction (MI). Selective serotonin reuptake inhibitors reduce this risk. The site of action is the serotonin transporter (SLC6A4), which is expressed in brain and blood cells. A functional polymorphism in the promoter region of the SLC6A4 gene has been described. This polymorphism may be associated with the risk of MI. The SLC6A4 polymorphism has been investigated by polymerase chain reaction in 671 male patients with MI and in 688 controls from the Etude Cas-Témoins de l'Infarctus du Myocarde (ECTIM) multicentric study. Percentages for LL, LS, and SS genotypes were 35.5%, 45.4%, and 19.1%, respectively, for cases versus 28.1%, 49.1%, and 22.8%, respectively, for controls. S allele frequency was 41.8% and 47.4% for cases and controls, respectively. After adjustment for age and center by using multivariable logistic regression, the odds ratio for MI associated with the LL genotype was 1.40 (95% CI 1.11 to 1.76, P=0.0047). The LL genotype of the SLC6A4 polymorphism is associated with a higher risk of MI. This could be attributable to the effect of the polymorphism on serotonin-mediated platelet activation or smooth muscle cell proliferation or on other risk factors, such as depression or response to stress.

  4. Etudes sur l'histoire de la pauvreté (Moyen Age — XVIe siècle

    Directory of Open Access Journals (Sweden)

    Hilário Franco Júnior


    Full Text Available MOLLAT, Michel (dir..  Etudes sur l'histoire de la pauvreté (Moyen Age — XVIe siècle. 2 vols. Paris Publications de la Sorbonne, 1974. 855p. (primeiro parágrafo do artigo Esta obra reúne alguns dos trabalhos desenvolvidos nos seminários sobre pobres e pobreza na Idade Média, que o professor Michel Mollat coordena desde 1962 na Sorbonne. Após um rápido e excelente ensaio introdutório, assinado pelo organizador da obra, no qual se colocam alguns dos problemas relativos ao estudo da pobreza medieval, seguem-se 35 estudos, devidos a diferentes colaboradores. O primeiro volume, correspondente à primeira parte da obra ("Pobreza e caridade, valores individuais" agrupa 21 estudos, e o segundo ("Desenvolvimento da pobreza e organização da assistência". Uma bibliografia de cerca de 160 títulos, uma lista de palavras-chaves latinas de uso mais comum na documentação da Idade Média e algumas gravuras extra-texto de boa qualidade completam o livro.

  5. Contribution a l'etude et au developpement de nouvelles poudres de fonte (United States)

    Boisvert, Mathieu

    " uphill " permet de conserver plus ou moins de graphite nodulaire a l'interieur des regions riches en silicium, alors que le reste du graphite precipite sous forme lamellaire/vermiculaire dans les regions interparticulaires. L'etude des poudres de fontes et la recherche des mecanismes regissant la morphologie du graphite dans les fontes coulees/moulees nous ont amenes a produire des poudres de fontes traitees au magnesium avant l'atomisation. Plusieurs resultats fondamentaux ont ete obtenus de la caracterisation des poudres traitees au magnesium et de leur comparaison avec des poudres de chimies similaires non traitees au magnesium. D'abord, il a ete possible d'observer des bifilms d'oxyde de silicium dans la structure du graphite primaire d'une poudre de fonte grise hypereutectique. Il s'agit des premieres images montrant la structure double de ces defauts, venant ainsi appuyer la theorie elaboree par le professeur John Campbell. Ensuite, il a ete montre que le traitement au magnesium forme une atmosphere protectrice gazeuse autogeneree qui empeche l'oxydation de la surface du bain liquide et donc, la formation et l'entrainement des bifilms. Le role du magnesium sur la morphologie du graphite est de diminuer le soufre en solution en formant des precipites de sulfure de magnesium et ainsi d'augmenter l'energie d'interface graphite-liquide. En reponse a cette grande energie d'interface graphite-liquide, le graphite cherche a minimiser son ratio surface/volume, ce qui favorise la formation de graphite spheroidal. De plus, deux types de germination ont ete observes dans la poudre de fonte hypereutectique traitee au magnesium. Le premier type est une germination heterogene sur un nombre limite de particules faites de magnesium, d'aluminium, de silicium et d'oxygene. Le deuxieme type est une germination homogene des nodules dans certaines regions du liquide plus riches en silicium. L'observation du centre reel tridimensionnel, en microscopie electronique en transmission en

  6. Study of current instabilities in high resistivity gallium arsenide; Etude des instabilites de courant dans l'arseniure de gallium de haute resistivite

    Energy Technology Data Exchange (ETDEWEB)

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


    We have shown the existence and made a study of the current oscillations produced in high-resistivity gallium arsenide by a strong electric field. The oscillations are associated with the slow travelling of a region of high electrical field across the whole sample. An experimental study of the properties of these instabilities has made it possible for us to distinguish this phenomenon from the Gunn effect, from acoustic-electric effects and from contact effects. In order to account for this type of instability, a differential trapping mechanism involving repulsive impurities is proposed; this mechanism can reduce the concentration of charge carriers in the conduction band at strong electrical fields and can lead to the production of a high-field domain. By developing this model qualitatively we have been able to account for all the properties of high-resistance gallium arsenide crystals subjected to a strong electrical field: increase of the Hall constant, existence of a voltage threshold for these oscillations, production of domains of high field, low rate of propagation of these domains, and finally the possibility of inverting the direction of the propagation of the domain without destroying the latter. A quantitative development of the model makes it possible to calculate the various characteristic parameters of these instabilities. Comparison with experiment shows that there is a good agreement, the small deviations coming especially from the lack of knowledge concerning transport properties in gallium arsenide subjected to high fields. From a study of this model, it appears that the instability phenomenon can occur over a wide range of repulsive centre concentrations, and also for a large range of resistivities. This is the reason why it appears systematically in gallium arsenide of medium and high resistivity. (authors) [French] Nous avons mis en evidence et etudie des oscillations de courant qui se produisent a champ electrique eleve dans l

  7. Controlling Water Intercalation Is Key to a Direct Graphene Transfer. (United States)

    Verguts, Ken; Schouteden, Koen; Wu, Cheng-Han; Peters, Lisanne; Vrancken, Nandi; Wu, Xiangyu; Li, Zhe; Erkens, Maksiem; Porret, Clement; Huyghebaert, Cedric; Van Haesendonck, Chris; De Gendt, Stefan; Brems, Steven


    The key steps of a transfer of two-dimensional (2D) materials are the delamination of the as-grown material from a growth substrate and the lamination of the 2D material on a target substrate. In state-of-the-art transfer experiments, these steps remain very challenging, and transfer variations often result in unreliable 2D material properties. Here, it is demonstrated that interfacial water can insert between graphene and its growth substrate despite the hydrophobic behavior of graphene. It is understood that interfacial water is essential for an electrochemistry-based graphene delamination from a Pt surface. Additionally, the lamination of graphene to a target wafer is hindered by intercalation effects, which can even result in graphene delamination from the target wafer. For circumvention of these issues, a direct, support-free graphene transfer process is demonstrated, which relies on the formation of interfacial water between graphene and its growth surface, while avoiding water intercalation between graphene and the target wafer by using hydrophobic silane layers on the target wafer. The proposed direct graphene transfer also avoids polymer contamination (no temporary support layer) and eliminates the need for etching of the catalyst metal. Therefore, recycling of the growth template becomes feasible. The proposed transfer process might even open the door for the suggested atomic-scale interlocking-toy-brick-based stacking of different 2D materials, which will enable a more reliable fabrication of van der Waals heterostructure-based devices and applications.

  8. Organized monolayers of biological macromolecules on Au(111) surfaces

    DEFF Research Database (Denmark)

    Zhang, Jingdong; Chi, Qijin; Nielsen, Jens Ulrik


    Single-crystal electrochemistry and scanning tunneling microscopy directly in aqueous electrolyte solution (in situ STM) are established in physical electrochemistry but new in studies of adsorption and interfacial electrochemistry of biological macromolecules. These high-resolution techniques ha...

  9. Direct electron transfer of xanthine oxidase and its catalytic reduction to nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Wu Yunhua [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Key Lab for Biotechnology of National Commission for Nationalities, College of Life Science, the South Central University for Nationalities, Wuhan 430074 (China); Hu Shengshui [Department of Chemistry, Wuhan University, Wuhan 430072 (China)], E-mail:


    This work reports on the direct electrochemistry of the xanthine oxidase (XO) from buttermilk, a mononuclear molybdenum enzyme that comprises four redox active cofactors: a five-coordinate mononuclear Mo ion, two [2Fe-2S] clusters, and a flavin adenine dinucleotide (FAD) group. The Mo, [2Fe-2S] and FAD redox responses are obtained from the enzyme immobilized on an activated single-wall carbon nanotubes (SWNTs) modified glassy carbon electrode using protein film voltammetry. The formal potentials of which are -0.61 V, -0.47 V and -0.37 V (vs. SCE) at pH 5.0, respectively. Upon addition of nitrate to the electrochemical cell, a steady-state voltammogram and i-t amprometric response were observed, indicating XO can catalyze the reduction of nitrate.

  10. Surface analysis and electrochemistry of a robust carbon-nanofiber-based electrode platform H{sub 2}O{sub 2} sensor

    Energy Technology Data Exchange (ETDEWEB)

    Suazo-Dávila, D.; Rivera-Meléndez, J. [NASA-MIRO Center for Advanced Nanoscale Materials (CANM), Department of Chemistry, Molecular Sciences Research Center, University of Puerto Rico, Río Piedras Campus, San Juan, PR, 00936 (United States); Koehne, J.; Meyyappan, M. [Center for Nanotechnology, NASA Ames Research Center, Moffett Field, CA 94035 (United States); Cabrera, C.R., E-mail: [NASA-MIRO Center for Advanced Nanoscale Materials (CANM), Department of Chemistry, Molecular Sciences Research Center, University of Puerto Rico, Río Piedras Campus, San Juan, PR, 00936 (United States)


    Highlights: • Vertically aligned carbon nanofibers were intercalated with SiO{sub 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{sup −2} mM{sup −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.

  11. Battery Relevant Electrochemistry of Ag7Fe3(P2O7)4 : Contrasting Contributions from the Redox Chemistries of Ag+ and Fe3+

    International Nuclear Information System (INIS)

    Zhang, Yiman; Marschilok, Amy C.; Stony Brook University, NY; Takeuchi, Esther S.


    Ag 7 Fe 3 (P 2 O 7 ) 4 is an example of an electrochemical displacement material which contains two different electrochemically active metal cations, where one cation (Ag + ) forms metallic silver nanoparticles external to the crystals of Ag 7 Fe 3 (P 2 O 7 ) 4 via an electrochemical reduction displacement reaction, while the other cation (Fe +3 ) is electrochemically reduced with the retention of iron cations within the anion structural framework concomitant with lithium insertion. These contrasting redox chemistries within one pure cathode material enable high rate capability and reversibility when Ag 7 Fe 3 (P 2 O 7 ) 4 is employed as cathode material in a lithium ion battery (LIB). Further, pyrophosphate materials are thermally and electrically stable, desirable attributes for cathode materials in LIBs. In this article, a bimetallic pyrophosphate material Ag 7 Fe 3 (P 2 O 7 ) 4 is synthesized and confirmed to be a single phase by Rietveld refinement. Electrochemistry of Ag 7 Fe 3 (P 2 O 7 ) 4 is reported for the first time in the context of lithium based batteries using cyclic voltammetry and galvanostatic discharge–charge cycling. The reduction displacement reaction and the lithium (de)insertion processes are investigated using ex situ X-ray absorption spectroscopy and X-ray diffraction of electrochemically reduced and oxidized Ag 7 Fe 3 (P 2 O 7 ) 4 . Ag 7 Fe 3 (P 2 O 7 ) 4 exhibits good reversibility at the iron centers indicated by ~80% capacity retention over 100 cycles following the initial formation cycle and excellent rate capability exhibited by ~70% capacity retention upon a 4-fold increase in current.

  12. Bottom-up approach for the reaction of xenobiotics and their metabolites with model substances for natural organic matter by electrochemistry-mass spectrometry (EC-MS). (United States)

    Chen, Lei; Hofmann, Diana; Klumpp, Erwin; Xiang, Xinyi; Chen, Yingxu; Küppers, Stephan


    Risk assessment of xenobiotics requires a comprehensive understanding of their transformation in the environment. As most of the transformation processes usually involve a redox reaction or a hydrolysis as the first steps of the transformation, we applied an approach that uses an electrochemical cell to investigate model "redox" reactions in aqueous solutions for environmental processes. We investigated the degradation of a variety of xenobiotics from polar to nonpolar and analyzed their degradation products by on-line coupling of electrochemistry with mass spectrometry (EC-MS). Furthermore, we evaluated possible binding reactions with regard to the generation of non-extractable residues with some model substances (catechol, phthalic acid, γ-L-Glutamyl-L-cysteinyl-glycine (GSH) and L-histidine) deduced from a natural organic matter (NOM) structure model and identified possible binding-sites. Whereas typically investigations in soil/water-systems have been applied, we used to our knowledge for the first time a bottom-up approach, starting from the chemicals of interest and different model substances for natural organic matter to evaluate chemical binding mechanisms (or processes) in the EC-MS under redox conditions. Under oxidative conditions, bindings of the xenobiotics with catechol, GSH and histidine were found, but no reactions with the model compound phthalic acid were observed. In general, no chemical binding has yet been found under reductive conditions. In some cases (i.e. benzo[a]anthracene) the oxidation product only underwent a binding reaction, whereas the xenobiotic itself did not undergo any reactions. EC-MS is a promising fast and simple screening method to investigate the environmental behavior of xenobiotics and to evaluate the potential risks of newly synthesized substances. Copyright © 2012 Elsevier Ltd. All rights reserved.

  13. Redox-induced ion pairing of anionic surfactants with ferrocene-terminated self-assembled monolayers: Faradaic electrochemistry and surfactant aggregation at the monolayer/liquid interface. (United States)

    Dionne, Eric R; Sultana, Tania; Norman, Lana L; Toader, Violeta; Badia, Antonella


    Oxidoreduction of self-assembled monolayers (SAMs) of ferrocenyldodecanethiolate on gold in aqueous solutions of surface-active sodium n-alkyl sulfates (NaCnSO4) of 6, 8, 10, and 12 carbons is investigated by cyclic voltammetry and surface plasmon resonance. The effects of surfactant micellization and alkyl chain length on the redox response of the surface-tethered ferrocenes are examined. The SAM redox electrochemistry is sensitive to the surfactant aggregation state in solution. The nonideal behavior of the sodium alkyl sulfates at concentrations above the critical micelle concentration leads to a non-Nernstian variation of the SAM redox potential with concentration. The presence of micelles in solution results in decreased anodic-to-cathodic peak separations and anodic peak full widths at half-maximum. A longer alkyl chain length results in an increased ability of the alkyl sulfate anion to ion pair with the SAM-bound ferrocenium, resulting in oxidation of the ferrocene at lower potential. A comparison of the SAM redox potential at a fixed surfactant concentration of ideal behavior suggests a 4.5 × 10(4) difference in the ion-pairing abilities of the shorter-chain C6SO4(-) and longer-chain C12SO4(-). One-half of the available SAM-bound ferrocenes are oxidized in the NaCnSO4 electrolyte. Surfactant anions adsorb and assemble onto the SAM surface by specific ion-pairing interactions between the sulfate headgroups and oxidized ferrocenium species, forming an interdigitated monolayer in which the surfactant anions alternate between a heads-down and heads-up orientation with respect to the SAM. The work presented points to applications of ferrocenylalkanethiolate SAMs as anion-selective membranes, probes of micelle formation, and surfaces for the electrochemically switchable assembly of organosulfates.

  14. Superficial characterization and zircaloy-2 electrochemistry with hydrothermal deposit of platinum; Caracterizacion superficial y electroquimica de zircaloy-2 con deposito hidrotermal de platino

    Energy Technology Data Exchange (ETDEWEB)

    Contreras R, A.; Arganis J, C. R.; Medina A, A. L. [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Gris C, M. M., E-mail: [Comision Federal de Electricidad, Central Nucleoelectrica Laguna Verde, Carretera Cardel-Nautla Km 42.5, Alto Lucero, Veracruz (Mexico)


    The combustible elements of the boiling water nuclear reactors (BWR) are formed by zircaloy-2 tubes that contain in their interior UO{sub 2} pellets. With the objective of mitigating the speed of crack growth by IGSCC to a minimum negative impact on the BWR operation, General Electric developed the noble metals chemical addition (NMCA), in where noble metals particles as Pt, Pd, and Rh, are deposited on the surface of the metal to catalyze the recombination of H{sub 2} and O{sub 2}. Hydrogen is also injected to have it in excess and to favor this recombination (HWC) and zinc to reduce dose. In this work was oxidized zircaloy-2 low similar conditions to the HWC, platinum was deposited starting from a solution of Na{sub 2}Pt(OH){sub 6} with 30 ppm of Pt, in refined samples and without polishing, they were characterized by scanning electron microscopy, energy dispersed spectroscopy, XPS and electrochemistry, by means of Tafel curves and cyclical polarization. On the zircaloy surface was found a ZrO{sub 2} layer that remains under the different study conditions. Under HWC conditions is the oxides formation, possibly complex oxides of zirconium, iron and tin. After the platinum deposit these oxides decrease forming the sub-oxides: Zr{sub 2}O, Zr O, Zr{sub 2}O{sub 3}. The Tafel curves indicates the reduction of the oxygen of the sample with platinum and the cyclical polarization curves show that the reactions that happen on the zircaloy electrodes are not dur to located corrosion. (Author)

  15. Electrochemistry and biosensing reactivity of heme proteins adsorbed on the structure-tailored mesoporous Nb2O5 matrix

    International Nuclear Information System (INIS)

    Xu Xin; Tian Bozhi; Zhang Song; Kong Jilie; Zhao Dongyuan; Liu Baohong


    The highly ordered mesoporous niobium oxides fabricated by self-adjusted synthesis have been used as immobilization matrices of heme proteins including Cytochrome c (Cyt C) and horseradish peroxidase (HRP) for their large surface areas, narrow pore size distributions and good biocompatibility. The assembling process was investigated by cyclic voltammetry, amperometry and potential step chronoamperometry in details. Niobium oxide matrices with different structural features were templated with the surfactants and the selectivity of these hosts to specific protein characteristics was determined. It was observed that proteins could be readily assembled onto the mesoporous films with detectable retention of bioactivity. The Nb 2 O 5 matrix with a tailored pore size and counterpoised surface charge to that of hemes allowed for a maximum adsorption capacity of biomolecules. The adsorbed redox molecules exhibited direct electrochemical behavior and gave a pair of well-defined quasi-reversible cyclic voltammetric peaks, indicating that the mesoporous niobium oxide matrix could effectively promote the direct electron transfer between the protein redox site adsorbed and the electrode surface. The midpoint redox potentials of adsorbed Cyt-c and HRP were 14 and -122 mV versus SCE, respectively. Furthermore, the immobilized HRP onto Nb 2 O 5 derived electrode presented good bioactivity and thus was fabricated as an amperometric biosensor for the response of hydrogen peroxide in the range from 0.1 μM to 0.1 mM

  16. Electrochemistry, a technique to prepare redox nano-structured composite materials (polymer/nano-particles) - Characterizations - Applications; L'electrochimie, un outil pour elaborer des materiaux composites redox nanostructures (polymere/nanoparticules) - Caracterisations - Applications

    Energy Technology Data Exchange (ETDEWEB)

    Chardon-Noblat, S. [Grenoble-1 Univ. Joseph Fourier, Lab. d' Electrochimie Organique et de Photochimie Redox, UMR 5630, Institut de Chimie Moleculaire de Grenoble, FR CNRS 2607, 38 - Grenoble (France)


    In this work is presented at first the preparation by an electrochemical way of bi functional nano-structured composite materials. It is shown that with the pulsed electrolysis techniques, it is possible to obtain metallic particles whose size and organization are controlled at the nano-scopic scale in redox matrices. Then, are presented the physico-chemical characterizations of these nano-objects (coupled in situ or ex situ at the electrochemistry). The first results relative to the catalytic activation of CO{sub 2} with these materials used as composite cathodes are indicated. (O.M.)

  17. Etude energetique et modelisation d'un Systeme Hybride Eolien-Diesel avec stockage d'Air Comprime (SHEDAC) (United States)

    Martinez, Nicolas

    Actuellement le Canada et plus specialement le Quebec, comptent une multitude de sites isoles dont !'electrification est assuree essentiellement par des generatrices diesel a cause, principalement, de l'eloignement du reseau central de disuibution electrique. Bien que consideree comme une source fiable et continue, 1 'utilisation des generatrices diesel devient de plus en plus problematique d'un point de vue energetique, economique et environnemental. Dans le but d'y resoudre et de proposer une methode d'approvisionnement plus performante, mains onereuse et plus respectueuse de l'environnement, l'usage des energies renouvelables est devenu indispensable. Differents travaux ont alors demontre que le couplage de ces energies avec des generauices diesel, formant des systemes hybrides, semble etre une des meilleures solutions. Parmi elles, le systeme hybride eolien-diesel avec stockage par air comprime (SHEDAC) se presente comme une configuration optimale pour 1 'electrification des sites isoles. En effet, differentes etudes ont permis de mettre en avant l'efficacite du stockage par air comprime, par rapport a d'autres technologies de stockage, en complement d'un systeme hybride eolien-diesel. Plus precisement, ce systeme se compose de sous-systemes qui sont: des eoliennes, des generatrices diesel et une chaine de compression et de stockage d'air comprime qui est ensuite utilisee pour suralimenter les generatrices. Ce processus permet ainsi de reduire Ia consommation en carburant tout en agrandissant la part d'energie renouvelable dans Ia production electrique. A ce jour, divers travaux de recherche ont pennis de demontrer I' efficacite d 'un tel systeme et de presenter une variete de configurations possibles. A travers ce memoire, un logiciel de dimensionnement energetique y est elabore dans le but d'unifom1iser !'approche energetique de cette technologie. Cet outil se veut etre une innovation dans le domaine puisqu'il est actuellement impossible de dimensionner un

  18. Composes inter-halogenes sous pression: etude des transformations structurales dans le monobromure d'iode sous forme dense (United States)

    Bouchard, Alexandre

    La famille des composes halogenes et inter-halogenes representent des solides moleculaires adoptant des phases denses communes avec des solides moleculaires diatomiques comme l'azote et l'hydrogene. Parmi les transformations structurales et electroniques induites sous haute pression et observees dans ces solides, on note, entre autres, la dissociation moleculaire et la metallisation. De plus, l'etude des phases denses de l'iode a permis recemment l'observation d'une structure cristalline possedant une modulation dite incommensurable, c'est-a-dire une modulation possedant une periodicite differente de celle de la structure cristalline, jetant ainsi une lumiere nouvelle sur le processus de dissociation moleculaire dans les solides halogenes. Dans ce memoire, on propose d'etudier les changements structuraux dans monobromure d'iode (IBr), un compose inter-halogene possedant des proprietes structurales semblables a celles de deux composes halogenes, soit l'iode (I 2) et le brome (Br2) sous leur forme solide. Des experiences de diffraction des rayons X de poudres en utilisant un rayonnement synchrotron ont ete realisees a temperature ambiante sur l'IBr en variant la pression jusqu'aux environs de 60 GPa. La nature chimique particuliere du compose IBr a necessite la mise au point de techniques de chargement d'echantillon destinees a preserver l'integrite chimique de la substance utilisee. On rapporte egalement l'observation d'une phase de l'IBr presentant une modulation incommensurable. Les phases observees dans l'IBr permettent d'etablir des paralleles avec les phases denses rapportees dans I2 et Br2 par le biais d'un modele phenomenologique decrivant la sequence structurale des solides halogenes sous forme condensee.

  19. Systematic study of plasma and serum proteins in the pig; Etude systematique des proteines plasmatiques et seriques du porc

    Energy Technology Data Exchange (ETDEWEB)

    Daburon, F.; Nizza, P.; Hatchikian, C.; Schmidt, J.-P. [Commissariat a l' Energie Atomique (France)


    This work has been carried out in the framework of the determination of the physiological constants of a normal pig. The aim was to study the serum and plasma proteins of this animal species, the ultimate object being to discover whether the qualitative and quantitative changes in these proteins can make a significant contribution to the establishment of a biological dosimetry for irradiated pigs. The serum and plasma from a normal pig were analyzed first by various simple electrophoretic methods and then by immuno-electrophoresis. As a result of the particular characteristics of pig serum we have gradually been led to make numerous modifications to the techniques used for human serums or for those of small laboratory animals. Much careful work and patience were required in order to obtain reproducible results. (authors) [French] Ce travail se situe dans le cadre de la determination des constantes physiologiques du porc normal. il s'agissait de proceder a l'etude des proteines seriques et plasmatiques de cette espece animale, le but ulterieur etant de savoir si les modifications qualitatives et quantitatives de ces proteines pourront representer une contribution valable a l'etablissement d'une dosimetrie biologique chez le porc irradie. Le serum et le plasma du porc normal ont ete analyses d'abord par diverses methodes electrophoretiques simples puis par immunoelectrophorese. Les caracteristiques particulieres du serum de porc nous ont conduits a apporter progressivement de nombreuses modifications aux techniques utilisees pour des serums humains ou de petits animaux de laboratoire. L'obtention de resultats reproductible a exige beaucoup de patience et de minutie. (auteurs)

  20. Synthesis and Electrochemistry of Li3MnO4: Mn in the +5 OxidationState

    Energy Technology Data Exchange (ETDEWEB)

    Saint, Juliette.A.; Doeff, Marca M.; Reed, John


    Computational and experimental work directed at exploringthe electrochemical properties of tetrahedrally coordinated Mn in the +5oxidation state is presented. Specific capacities of nearly 700 mAh/g arepredicted for the redox processes of LixMnO4 complexes based on twotwo-phase reactions. One is topotactic extractionof Li from Li3MnO4 toform LiMnO4 and the second is topotactic insertion of Li into Li3MnO4 toform Li5MnO4. In experiments, it is found that the redox behavior ofLi3MnO4 is complicated by disproportionation of Mn5+ in solution to formMn4+ and Mn7+ and byother irreversible processes; although an initialcapacity of about 275 mAh/g in lithiumcells was achieved. Strategiesbased on structural considerations to improve the electrochemicalproperties of MnO4n- complexes are given.

  1. Electrochemistry and electrochemiluminescence of [Ru(II)-tris(bathophenanthroline-disulfonate)]4- in aprotic conditions and aqueous buffers. (United States)

    Zanarini, Simone; Della Ciana, Leopoldo; Marcaccio, Massimo; Marzocchi, Ettore; Paolucci, Francesco; Prodi, Luca


    In this work, the electrochemical and ECL properties of tris[1,10-phenanthrolinediyl-4,7-di(benzenesulfonate)]Ru(II) ([Ru(BPS)3]4-) have been addressed in both strictly aprotic conditions and aqueous buffers. A combined theoretical and experimental approach is presented to focus thermodynamics and kinetic effects of electro-generated species possessing highly negative charge. The complex, prepared as the sodium salt by using a newly developed procedure, was subsequently converted to the tetrabutylammonium salt by ion exchange, thus making it soluble in organic media and allowing, for the first time, its thorough electrochemical investigation in ultra-dry aprotic media. The electrochemically induced luminescence (ECL) of Na 4[Ru(BPS)3] in phosphate buffer, using the co-reactant method (tripropylamine), was investigated as a function of the electrode material and halide addition, and ECL intensities six times higher than that of [Ru(bpy)3]2+ were found. In addition, the ECL behavior of this promising dye for biomolecule recognition was investigated in aprotic media and, for the first time, the direct radical anion-radical cation annihilation ECL was obtained.

  2. F{sup 19} relaxation in non-magnetic hexafluorides; Contribution a l'etude de la relaxation des fluors dans les hexafluorures non magnetiques

    Energy Technology Data Exchange (ETDEWEB)

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


    The interesting properties of the fluorine magnetic resonance in the hexafluorides of molybdenum, tungsten and uranium, are very much due to large anisotropies of the chemical shift tensors. In the solid phases these anisotropies, the values of which are deduced from line shape studies, allow one to show that the molecules undergo hindered rotations about the metal atom. The temperature and frequency dependence of the fluorine longitudinal relaxation times shows that the relaxation is due to the molecular motion. The dynamical parameters of this motion are then deduced from the complete study of the fluorine relaxation in the rotating frame. In the liquid phases, the existence of anisotropies allows an estimation of the different contributions to the relaxation. In particular, the frequency and temperature dependence of the relaxation shows it to be dominated by the spin-rotation interaction. We have shown that the strength of this interaction can be deduced from the chemical shifts, and the angle through which the molecule rotates quasi-freely can be determined. In the hexafluorides, this angle is roughly one radian at 70 C, and with the help of this value, the friction coefficients which describe the intermolecular interactions are discussed. (author) [French] Les proprietes de la resonance magnetique des fluors dans les hexafluorures de molybdene, tungstene et uranium sont influencees par l'existence de deplacements chimiques tres anisotropes. Dans les phases solides, la valeur de cette anisotropie peut etre determinee par l'analyse des formes de raies et son existence permet de montrer que les molecules sont en rotation empechee autour de leur atome central. L'etude du temps de relaxation longitudinal en fonction de la temperature et de la frequence montre que la relaxation est due aux mouvements moleculaires, aux plus hautes temperatures. Les proprietes dynamiques du mouvement sont obtenues par l'etude complete de la relaxation spin

  3. Structural Defects of Silver Hollandite, Ag(x)Mn8O(y), Nanorods: Dramatic Impact on Electrochemistry. (United States)

    Wu, Lijun; Xu, Feng; Zhu, Yimei; Brady, Alexander B; Huang, Jianping; Durham, Jessica L; Dooryhee, Eric; Marschilok, Amy C; Takeuchi, Esther S; Takeuchi, Kenneth J


    Hollandites (OMS-2) are an intriguing class of sorbents, catalysts, and energy storage materials with a tunnel structure permitting one-dimensional insertion and deinsertion of ions and small molecules along the c direction. A 7-fold increase in delivered capacity for Li/AgxMn8O16 electrochemical cells (160 versus 23 mAh/g) observed upon a seemingly small change in silver content (x ∼1.1 (L-Ag-OMS-2) and 1.6 (H-Ag-OMS-2)) led us to characterize the structure and defects of the silver hollandite material. Herein, Ag hollandite nanorods are studied through the combined use of local (atomic imaging, electron diffraction, electron energy-loss spectroscopy) and bulk (synchrotron based X-ray diffraction, thermogravimetric analysis) techniques. Selected area diffraction and high resolution transmission electron microscopy show a structure consistent with that refined by XRD; however, the Ag occupancy varies significantly even within neighboring channels. Both local and bulk measurements indicate a greater quantity of oxygen vacancies in L-Ag-OMS-2, resulting in lower average Mn valence relative to H-Ag-OMS-2. Electron energy loss spectroscopy shows a lower Mn oxidation state on the surface relative to the interior of the nanorods, where the average Mn valence is approximately Mn(3.7+) for H-Ag-OMS-2 and Mn(3.5+) for L-Ag-OMS-2 nanorods, respectively. The higher delivered capacity of L-Ag-OMS-2 may be related to more oxygen vacancies compared to H-Ag-OMS-2. Thus, the oxygen vacancies and MnO6 octahedra distortion are assumed to open the MnO6 octahedra walls, facilitating Li diffusion in the ab plane. These results indicate crystallite size and surface defects are significant factors affecting battery performance.

  4. Conservation of an ion beam brightness. Study of a non brightness disturbing lens; Conservation de la brillance d'un faisceau ionique. Etude d'une lentille ne deteriorant pas cette brillance

    Energy Technology Data Exchange (ETDEWEB)

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


    Experimental studies of ion sources prove that large initial brightnesses can be obtained by using the plasma expansion principle. However these brightnesses are usually spoiled by the beam focusing and accelerating systems. A high intensity focusing set up is first theoretically studied, then numerically determined by use of a 7094 IBM computer. Aberrations have been minimized. It has then been possible to construct a set up conserving the source initial brightness. For a 100 mA beam the focusing voltage is 150 kV, the beam study has been done for 350 keV beam final energy. Given is a discussion of results. (author) [French] L'etude experimentale des sources d'ions, montre que de grandes brillances initiales peuvent etre atteintes en utilisant le principe de l'expansion du plasma. Mais generalement ces brillances sont alterees par la focalisation et l'acceleration du faisceau. Nous presentions une etude theorique, suivie d'une determination numerique utilisant l'ordinateur IBM 7094, d'un montage capable de focaliser des intensites elevees. Nous nous efforcons de reduire au minimum les aberrations. Nous avons pu realiser un systeme conservant la brillance initiale de la source. Pour une intensite de 100 mA la tension de focalisation doit etre de 150 kV. L'etude du faisceau a ete faite a 350 keV. Nous discutons enfin des resultats obtenus. (auteur)

  5. Contribution to the study of the stability of water-cooled reactors; Contribution a l'etude de la stabilite des reacteurs refroidis par de l'eau

    Energy Technology Data Exchange (ETDEWEB)

    Coudert, C. [Commissariat a l' Energie Atomique, Cadarache (France). Centre d' Etudes Nucleaires


    This work is devoted to the study of the stability of reactors cooled by water subjected only to natural convection. It is made up of two parts, a theoretical study and experimental work, each of these parts being devoted to a consideration of linear and non-linear conditions: - calculation of the transfer function of the reactor using neutronic and hydrodynamic linear equations with the determination of the instability threshold; - demonstration of the existence of the limiting oscillation cycle in the case of a linear feedback using MALKIN'S method; - measurement and interpretation of the reactor's transfer functions and of the hydrodynamic transfer functions; and - analysis of the noise due to boiling. (author) [French] Dans ce travail on etudie la stabilite des piles refroidies par de l'eau circulant en convection naturelle. Cette etude se divise en deux parties: un travail theorique et un travail experimental, chacune de ces parties comportant une etude lineaire et une etude non-lineaire: - calcul de la fonction de transfert du reacteur a partir des equations lineaires de la neutronique et de l'hydrodynamique avec determination du seuil d'instabilite; - demonstration de l'existence du cycle limite des oscillations dans le cas d'une retroaction lineaire en utilisant la methode de MALKIN; - mesure et interpretation de la fonction de transfert du reacteur et des fonctions de transfert hydrodynamiques; et - analyse du bruit d'ebullition. (auteur)

  6. Part I: Virtual laboratory versus traditional laboratory: Which is more effective for teaching electrochemistry? Part II: The green synthesis of aurones using a deep eutectic solvent (United States)

    Hawkins, Ian C.

    The role of the teaching laboratory in science education has been debated over the last century. The goals and purposes of the laboratory are still debated and while most science educators consider laboratory a vital part of the education process, they differ widely on the purposes for laboratory and what methods should be used to teach laboratory. One method of instruction, virtual labs, has become popular among some as a possible way of capitalizing on the benefits of lab in a less costly and more time flexible format. The research regarding the use of virtual labs is limited and the few studies that have been done on General Chemistry labs do not use the virtual labs as a substitute for hands-on experiences, but rather as a supplement to a traditional laboratory program. This research seeks to determine the possible viability of a virtual simulation to replace a traditional hands-on electrochemistry lab in the General Chemistry II course sequence. The data indicate that for both content knowledge and the development of hands-on skills the virtual lab showed no significant difference in overall scores on the assessments, but that an individual item related to the physical set-up of a battery showed better scores for the hands-on labs over the virtual labs. Further research should be done to determine if these results are similar in other settings with the use of different virtual labs and how the virtual labs compare to other laboratories using different learning styles and learning goals. One often cited purpose of laboratory experiences in the context of preparing chemists is to simulate the experiences common in chemical research so graduate experience in a research laboratory was a necessary part of my education in the field of laboratory instruction. This research experience provided me the opportunity, to complete an organic synthesis of aurones using a deep eutectic solvent. These solvents show unique properties that make them a viable alternative to ionic

  7. Silicon P.I.N. Junctions used for studies of radiation damage; Etude de l'irradiation aux neutrons rapides du silicium au moyen de jonctions P.I.N

    Energy Technology Data Exchange (ETDEWEB)

    Lanore, J. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires


    Irradiation of silicon P.I.N. junction has been studied primarily for the purpose of developing a radiation damage dosimeter, but also for the purpose of investigating silicon itself. It is known that the rate of recombination of electrons and holes is a linear function of defects introduced by neutron irradiation. Two methods have been used to measure that rate of recombination: forward characteristic measurements, recovery time measurements. In order to explain how these two parameters depend on recombination rate we have given a theory of the P.I.N. junction. We have also given an idea of the carrier lifetime dependence versus temperature. Annealing effects in the range of 70 to 700 K have also been studied, we found five annealing stages with corresponding activation energies. As an application for these studies, we developed a radiation damage dosimeter with which we made several experiments in facilities such as Naiade or Marias. (author) [French] L'irradiation de structures P.I.N. etait faite dans le but d'etudier principalement la mise au point d'un dosimetre a ''radiation damage'' et aussi pour etudier plus profondement le silicium lui-meme. On sait que le taux de recombinaison electrons-trous est une fonction lineaire du taux de defauts introduits par irradiation aux neutrons. Deux methodes ont ete utilisees pour atteindre ce taux de recombinaison: mesures de la caracteristique directe, mesures du temps de retournement. Pour expliquer de quelle facon ces parametres dependent du taux de recombinaison. Nous avons donne une theorie de la jonction P.I.N. Nous avons aussi donne l'allure des variations du temps de vie des porteurs en fonction de la temperature. Nous avons d'autre part effectue des recuits entre 70 et 700 K, domaine dans lequel nous avons trouve cinq etapes de ''guerison'' avec les energies d'activation correspondantes. En application de ces etudes nous avons mis ou point un

  8. Some magnetic resonance properties of solutions of sodium in liquid ammonia; Contribution a l'etude des solutions de sodium dans l'ammoniac liquide par resonance magnetique

    Energy Technology Data Exchange (ETDEWEB)

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


    Dilute solutions of sodium in liquid ammonia are studied by the mean of dynamic polarization techniques, and with the aid of Becker Lindquist and Alder model. Paramagnetic shifts are computed as a function of the 'average spin density', for each of the nuclear spin system. The nuclear contributions to the Overhauser shift are computed in the same way. A theoretical study of the main relaxation processes is carried out for each of the nuclear spin system and for the electronic spin system. The dynamic polarization experiments consist in classical measurement of the Overhauser enhancement for nitrogen, and in direct measurements of nitrogen Knight shift and nuclear contributions to the Overhauser shift by the mean of double irradiation techniques. The results show that, in dilute solutions, the relaxation of nitrogen arises from quadrupole interaction and from hyperfine interaction with unpaired electrons. Both interactions are of the same order of magnitude. Overhauser shift measurements show that the spin density is negative at the proton site, in agreement with Hughes results. (author) [French] Les solutions diluees de sodium dans l'ammoniac sont etudiees au moyen des techniques de la polarisation dynamique, sur la base du modele de Becker Lindquist et Aider. Les deplacements paramagnetiques des raies de resonance nucleaire des differents noyaux sont analyses en faisant appel a la notion de ''densite moyenne de spin'' introduite par l'auteur; et les differentes contributions nucleaires au deplacement d'Overhauser sont calculees en fonction de cette meme grandeur. Une etude theorique de la relaxation de chaque systeme de spin permet d'evaluer l'importance relative des differents mecanismes mis en jeu. Les experiences de polarisation dynamique effectuees au cours de ce travail consistent en mesures classiques de l'effet Overhauser sur l'azote, d'une part, et en la mise en oeuvre de techniques

  9. The study of some thiazinic and indaminic dye syntheses induced by ionising radiation; Etude de quelques syntheses de colorants thianziniques et indaminiques amorcees par les rayonnements ionisants

    Energy Technology Data Exchange (ETDEWEB)

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


    With a view to finding some radiochemical reactions applicable on an industrial scale for evaluating the radioactive waste from nuclear reactors, a systematic study was made of the radiochemical synthesis of thiazinic dyes such as methylene blue and Lauths' violet, on which the first tests were carried out in 1954. The first part of the study concerned the identification and the dosage, during radiolysis, of dyes by means of their absorption spectra after separation from the reaction medium by adsorption chromatography or ion-exchange; other radiolysis products such as ammonium chloride and hydrogen peroxide were also identified. During a later stage by systematically varying the physico-chemical parameters it was possible to determine the most favourable conditions for radio-synthesis; the maximum radiochemical yields obtained had the following values: G (Lauths' violet) 1,65; G (Methylene blue) = 1,75. Furthermore, the study of the influence of variously substituted aminated products on the radiochemical yield showed the possibility of synthesising Bindsehedlers green and Wursters blue by radiochemical methods. Finally the discovery of a fundamental intermediate product, Wursters red, together with the kinetic study of the chemical synthesis of methylene blue made it possible to determine the main stages of the reaction mechanism and to decide which of these stages could be attributed to ionising radiations in the case of the radiochemical synthesis. (author) [French] Dans le but de trouver des reactions radiochimiques susceptibles d'une application industrielle pour valoriser les dechets radioactifs provenant des reacteurs nucleaires, il a ete entrepris une etude systematique de la synthese radiochimique des colorants thiazimiques tels que le Bleu de Methylene et le Violet de Lauth dont les premiers essais ont ete effectues par Loiseleur en 1954. La premiere partie de l'etude a porte sur l'identification et le dosage des colorants formes

  10. Magnetic study of solid uranium-fluorine complexes; Contribution a l'etude magnetique de composes fluores solides de l'uranium

    Energy Technology Data Exchange (ETDEWEB)

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


    A study of the magnetic susceptibility of uranium V fluorine complexes and of the magnetic resonance of fluorine atoms in uranium VI fluorine complexes has made it possible to put forward a structural model for these compounds for which it is impossible, because of the lack of suitable single crystals for X-ray diffraction work, to deduce the exact position of the fluorine atoms. It is shown that it is difficult to interpret the paramagnetism of uranium fluorides, because the uranium ions are in low-symmetry sites. A theoretical study of the magnetism of the U{sup V} ion in complex fluorides of the type M{sub 3}UF{sub 8} (M = NH{sub 4}, Na, Rb, Cs) leads to an interpretation based on a trigonal deformation of the eight fluorine atom structure surrounding the uranium atom. By applying a Hamiltonian spin formalism and making a systematic use of group theory, it is possible to present the susceptibility calculations very concisely. Study of the resonance and of the relaxation of the fluorine atoms in powdered uranium VI complex fluorides suggests a structural model in the case of NaUF{sub 7}. It is shown that the shape of the magnetic resonance absorption lines is strongly affected by the presence of large anisotropic chemical shifts. In the model proposed here, six fluorine atoms are linked to the uranium, atom by strongly covalent bonds in a deformed UF{sub 6} octahedral structure; the seventh fluorine atom remains ionic. The occurrence of a rotational movement of the octahedron is confirmed by a study of the longitudinal relaxation of the fluorine atoms, the activation energy being 0.46 eV. (author) [French] L'etude de la susceptibilite magnetique de complexes fluores d'uranium V et la resonance magnetique des fluors dans des complexes fluores d'uranium VI permettent de proposer un modele structural pour ces composes, ou la diffraction des rayons X, en l'absence de monocristaux convenables, est incapable de preciser la position des atomes de

  11. Experimental study of the hydrodynamic instabilities occurring in boiling-water reactors; Etude experimentale des instabilites hydrodynamiques survenant dans les reacteurs nucleaires a ebullition

    Energy Technology Data Exchange (ETDEWEB)

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


    The subjects is an experimental out-of pile loop study of the hydrodynamic oscillations occurring in boiling-water reactors. The study was carried out at atmospheric pressure and at pressure of about 8 atmospheres, in channels heated electrically by a constant and uniform specified current. In the test at 8 atmospheres the channel was a round tube of approximately 6 mm interior diameter. At 1 atmosphere a ring-section channel was used, 10 * 20 mm in diameter, with an inner heating tube and an outer tube of pyrex. It was possible to operate with natural convection and also with forced convection with test-channel by-pass. The study consists of 3 parts: 1. Preliminary determination of the laws governing pressure-drop during boiling. 2. Determination of the fronts at which oscillation appears, within a wide range of the parameters involved. 3. A descriptive study of the oscillations and measurement of the periods. The report gives the oscillation fronts with natural and forced convection for various values of the singular pressure drop at the channel inlet and for various riser lengths. The results are presented in non-dimensional form, which is available, in first approximation, for all geometric scales and for all fluids. Besides the following points were observed: - the wall (nature and thickness) can be an important factor ; - oscillation can occur in a horizontal channel. (author) [French] II a ete effectue une etude experimentale, en boucle hors-pile, des oscillations hydrodynamiques survenant dans les reacteurs a ebullition. L'etude a ete effectuee a la pression atmospherique et a une pression voisine de 8 atmospheres dans des canaux chauffes electriquement a puissance imposee constante et uniforme. Dans les essais a 8 atmospheres le canal etait un tube circulaire de diametre interieur 6 mm environ. A 1 atmosphere le canal etait de section annulaire 10 * 20 mm avec un tube interieur chauffant et un tube exterieur en pyrex. Le fonctionnement etait possible

  12. Nanostructured Iron and Manganese Oxide Electrode Materials for Lithium Batteries: Influence of Chemical and Physical Properties on Electrochemistry (United States)

    Durham, Jessica L.

    structural defects which facilitate Li+ diffusion through the tunnel walls and intimate electrochemical connection of bundled nanorods. Finally, a one-pot synthesis provided a series of AgFeO2/gamma-Fe 2O3 or AgxFeOy composites which, at the lowest silver regime (Ag0.2FeO1.6 ), exhibit 2X higher capacity than stoichiometric AgFeO2 and over 3X greater capacity than nanocrystalline gamma-Fe2O 3 after 50 cycles. Notably, mechanical mixing of AgFeO2 and gamma-Fe2O3 powders to mimic a one-pot Ag0.2FeO 1.6 composite yields lower delivered capacity and energy density where the results demonstrate the advantages of the directly prepared composite with more intimate particle connectivity not achievable through mechanical mixing.

  13. Study of point defects in pure iron by means of electrical resistivity; Etude au moyen de la resistivite electrique des defauts ponctuels dans le fer pur

    Energy Technology Data Exchange (ETDEWEB)

    Minier-Cassayre, C. [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires


    In the first part of this work, after having reviewed the production, observation and the annealing of point defects In metals, we resume the present state of research. In the second part, we explain the techniques we have employed to produce point defects at low temperatures: irradiation, quenching and cold-work; and go on to the study of their migration and annealing. The experimental results obtained for pure iron and for iron containing certain impurities are presented in the third part. In the fourth part we suggest a model which explains the different stages of annealing observed, and their properties. We then compare the energies of interaction between point defects with the values deduced from the theory of elasticity. (author) [French] Dans la premiere partie de cette etude, apres avoir passe en revue la production, l'observation et les modes de guerison des defauts ponctuels dans les metaux, nous exposons l'etat actuel des recherches. La seconde partie est consacree aux techniques que nous avons employees pour produire des defauts ponctuels a basse temperature: irradiations, trempe et ecrouissage puis a l'etude de leur migration et de leur guerison. Les resultats experimentaux obtenus dans le fer pur et le fer contenant certaines impuretes sont presentes dans le troisieme chapitre. Nous proposons ensuite un modele qui explique les differents stades de guerison observes et leurs nombreuses proprietes: nous comparons les energies d'interaction entre defauts ponctuels aux valeurs que l'on pourrait deduire d'un modele elastique. (auteur)

  14. Contribution to the study of deformed heavy nuclei by means of nuclear reactions; Contribution a l'etude des noyaux lourds deformes au moyen de reactions nucleaires

    Energy Technology Data Exchange (ETDEWEB)

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


    The experimental results obtained in the study of the (d,p) reactions, at E{sub d} = 12 MeV, on the three even-even deformed nuclei {sup 170}Yb, {sup 172}Yb and {sup 174}Yb have been analysed in terms of DWBA calculations. The spectroscopic information relative to the odd final nuclei have been compared with the predictions of the collective model and of the Nilsson's model. The effect of various parameters used in the DWBA analysis (form factors, optical wave functions) has been carefully studied. The observed differences between the three final nuclei are qualitatively reproduced in the experimental study of resonances, seen in excitation functions of elastically and inelastically scattered protons on the same target nuclei, and corresponding to analogue states in the three nuclei {sup 171}Lu, {sup 173}Lu and {sup 175}Lu. (author) [French] Les resultats experimentaux de l'etude des reactions (d.p) a E{sub d} = 12 MeV, sur les noyaux deformes pairs-pairs {sup 170}Yb, {sup 172}Yb et {sup 174}Yb ont ete interpretes dans le cadre de l'approximation de Born des ondes deformees. Les informations spectroscopiques relatives aux noyaux impairs finals ont ete comparees aux predictions du modele collectif et du modele de Nilsson, apres avoir examine avec soin l'influence des differents parametres (facteurs de forme, fonctions d'onde 'optiques') utilises lors de l'analyse. Les differences observees entre les trois noyaux finals sont qualitativement reproduites par les resultats experimentaux de l'etude de resonances dans les fonctions d'excitation de diffusion elastique et inelastique de protons sur les memes noyaux-cibles, lors de la recherche d'etats analogues dans les noyaux {sup 171}Lu, {sup 173}Lu et {sup 175}Lu. (auteur)

  15. Etude de l'equation de Navier-Stokes stochastique non homogene

    African Journals Online (AJOL)

    Resume. Le travail de cet article consiste a etudier !'existence et l'unicite de la solution des equations de Navier-Stokes stochastiques et non homogenes selon une methode directe due a Faedo-Galerkin [1]. Cette methode consiste a approcher les solutions de ces equations dans un espace de dimension finie. Dans ce ...

  16. Etude de la stabilite du processus d'usinage basee sur la theorie ...

    African Journals Online (AJOL)

    delay differential equation modeling machine tool chatter.PHD thesis. Budapest Universityof Technology and. Economics. [7]. Philip V. & Bayly. 2002. Effects of radial immersion and cutting direction on chatter instability in end- milling, American Society of Mechanical Engineers. Manufacturing Engineering Division., MED, ...

  17. Modeling and numerical study of two phase flow; Modelisation et etude numerique d'ecoulements diphasiques: 1- Modelisation d'un ecoulement homogene equilibre 2- Modelisation des collisions entre gouttelettes a l'aide d'un modele simplifie de type BGK

    Energy Technology Data Exchange (ETDEWEB)

    Champmartin, A.


    suivre une vitesse relative entre les deux phases et de prendre en compte deux vitesses) et sont supposees 'a l'equilibre en temperature et pression. Cette partie du manuscrit est composee de la derivation des equations, de l'ecriture d'un schema numerique associe a ce jeu d'equations, d'une etude d'ordre de ce schema ainsi que de simulations. Une etude mathematique de ce modele (hyperbolicite dans un cadre simplifie, stabilite du systeme lineaire autour d'un etat constant) a ete realisee dans un cadre ou le gaz est suppose barotrope. La seconde partie de ce manuscrit est consacree a la modelisation de l'effet de collisions inelastiques sur les gouttelettes lorsque l'on se place a un temps de simulation beaucoup plus court, pour lequel les gouttelettes ne peuvent plus etre vues comme un fluide. Pour modeliser ces collisions, on construit un modele simplifie (moins couteux en temps) de type BGK permettant de reproduire le comportement en temps de certains moments sur les gouttelettes. Ces moments sont choisis pour etre representatifs de l'effet des collisions sur ces gouttelettes, a savoir une thermalisation en vitesse et energie. Ce modele est discretise avec une methode particulaire et des resultats numeriques sont donnes en comparaison avec ceux obtenus avec un modele resolvant directement l'equation de Boltzmann homogene. (auteur)

  18. Etude des répercussions de la pollution industrielle sur la riziculture ...

    African Journals Online (AJOL)

    urbaine est exposée à la pollution industrielle. Les industries spécialisées dans le textile déversent leurs eaux usées dans le système d'irrigation, et polluent directement les champs de rizières à proximité des zones industrielles. Après 3 ans de ...

  19. Etude de l'équation de Navier-Stokes stochastique non homogène ...

    African Journals Online (AJOL)

    Le travail de cet article consiste à étudier l'existence et l'unicité de la solution des équations de Navier-Stokes Stochastiques et non homogènes selon une méthode directe due à Faedo-Galerkin [1]. Cette méthode consiste à approcher les solutions de ces équations dans un espace de dimension finie. Dans ce présent ...



    KADARI, Abdelhamid


    Depuis les temps les plus anciens, l’utilisation des plantes dans le domaine de la santé est toujours d’actualité (1), dans la mesure où elle représente une alternative sérieuse ou tout au moins un complément appréciable à la pharmacie classique issue de la chimie moderne. En effet, plus de 25 % des médicaments prescrits dans le monde entier dérivent directement ou indirectement des plantes (2). Cependant, en tant que sources de médicaments, les plantes restent encore sous plusieurs études, s...


    optimization of fuel cell electrodes. Hydrogen oxidation and reduction, the reduction of oxygen, and the oxidation of formic acid, a soluble organic...substance, were selected for these studiees because of their relevance to fuel cell systems and because of their relative simplicity. The electrodes


    DEFF Research Database (Denmark)

    Li, Qingfeng; Jensen, Jens Oluf; Bjerrum, Niels


    About 350 Papers Covering: Basics of Electrodes, Electrolytes, Cells, Batteries and Stacks, Measurement Techniques, Synthesis of Materials, Primary Batteries, Secondary Batteries, Supercapacitors, and Fuel Cells, Hydrogen Production and Storage, Photoelectrochemical Cells, Safety, Recycling...

  3. Etude expérimentale de la production de fer électrolytique en milieu alcalin: mécanisme de réduction des oxydes et développement d'une cellule


    Allanore , Antoine


    Iron is one of the few metals which is not industrially produced by electrolysis. The electrowinning of iron metal from its oxides in alkaline solution has been studied to develop such an ironmaking route. Two approaches have been adopted. The first one concerns the evaluation of the reaction mechanism. The study of iron ions electrochemistry in alkaline media shows that the electrodeposition of iron metal is possible. The study of a single iron oxide particle reduction reveals that a reactio...

  4. Etude exploratoire des conceptions de la circulation sanguine aupres d'eleves de l'ordre collegial (United States)

    Robitaille, Jean-Marc

    Il existe peu d'etudes sur les conceptions touchant les domaines de la biologie, notamment sur les conceptions de la circulation sanguine Nous avons observe egalement l'absence de recherche menee aupres d'eleves de l'ordre collegial sur cette question. Nous avons voulu combler une lacune en menant une recherche sur les conceptions de la circulation sanguine aupres d'eleves de l'ordre collegial. Pour mener cette recherche nous nous sommes inspires d'une methode developpee par Treagust (1988). Le premier niveau de formulation didactique etablit l'architecture du systeme et la fonction nutritive de la circulation. Le second niveau de formulation didactique decrit et relie les parametres de la dynamique de la circulation et leur relation: Pression, Debit et Resistance. Le troisieme niveau de formulation didactique s'interesse au controle de la circulation du sang dans un contexte d'homeostasie qui implique la regulation de la pression arterielle. Nous avons construit un questionnaire en nous guidant sur les niveaux de formulation didactique et l'analyse des entrevues menees aupres de dix-huit eleves, representatifs de la population cible. Ce questionnaire fut administre a un echantillon de 2300 eleves disperses dans six colleges de la region de Montreal. Notre echantillon comprend des eleves inscrits a des programmes de l'ordre collegial en Sciences de la nature et en Techniques de la sante et qui n'ont pas suivi le cours sur la circulation sanguine. Notre analyse des reponses des eleves de notre echantillon aux questions sur le premier niveau de formulation didactique revele que la majorite des eleves considerent que le systeme circulatoire relie les organes les uns aux autres dans un circuit en serie. Notre analyse revele egalement que la majorite des eleves estiment que les nutriments sont extraits du sang par les organes selon un processus de selection base sur les besoins determines par la fonction de l'organe. Ces besoins sont differents selon les organes qui ne

  5. Etude des transformations de phase dans les alliages de titane, 2; contribution à l'étude des transformation de l'alliage de titane TA6 V6 E2 en conditions isothermes après trempe à partir du domaine $(\\alpha + \\beta)$

    CERN Document Server

    Fontalirand, C; Fidelle, J P; Hocheid, B; Beauvais, C no 1; Fidelle, J P no 2; Hocheid, B no 2; Fontalirand, C no 1


    Etude des transformations de phase dans les alliages de titane, 2; contribution à l'étude des transformation de l'alliage de titane TA6 V6 E2 en conditions isothermes après trempe à partir du domaine $(\\alpha + \\beta)$

  6. Etude des phenomenes de penetration des especes chimiques dans les revetements cathodiques des cuves d'electrolyse de l'aluminium (United States)

    Brisson, Pierre-Yves

    Cette these decrit l'etude effectuee sur les phenomenes d'insertion du sodium et de penetration du bain electrolytique dans les revetements cathodiques des cuves d'electrolyse de l'aluminium. L'etude fut effectuee a l'aide d'un montage permettant d'effectuer l'electrolyse en laboratoire. Trois types de revetement cathodiques furent etudies : des blocs semi-graphitique, des blocs graphitiques et des blocs graphitises. L'insertion du sodium dans les trois differents types de blocs fut etudiee a l'aide de la spectrometrie des photoelectrons X (XPS). L'analyse a permis de mettre en evidence deux formes de sodium dans l'anthracite et la phase liante des materiaux semi-graphitiques et graphitiques, indiquant qu'une fraction du sodium se retrouve sous forme adsorbee dans les micropores des materiaux alors que l'autre fraction est inseree dans la structure cristalline du carbone. Dans les phases graphitiques (materiaux graphitises et graphitiques), seuls les micropores sont occupes par le sodium Ce resultat explique la tendance observee selon laquelle l'ajout de graphite dans les blocs permet d'abaisser le gonflement sodique. Les mecanismes de penetration du bain dans le reseau poreux des materiaux furent etudies en microscopie electronique et en diffraction des rayons X sur des echantillons apres differents temps d'electrolyses et en variant l'atmosphere (soit sous argon ou sous azote). Ces analyses ont permis d'identifier le mecanisme conduisant a la mouillabilite du bain sur le carbone en fonction de l'atmosphere entourant l'electrolyse. Ainsi, sous azote, la formation de NaCN dans les pores des materiaux par reactions entre le sodium et l'azote permet une mouillabilite accrue du bain alors qu'en absence d'azote (sous argon), le carbure d'aluminium, formes a la surface des pores, joue un role similaire. Dans ce dernier cas, la penetration du bain est moins rapide etant donnee la necessite de toujours amener des especes contenant de l'aluminium en tete du front de

  7. An overview of studies in structural mechanics; Panorama des etudes en mecanique des structures

    Energy Technology Data Exchange (ETDEWEB)

    Guilbaud, D.; Blay, N.; Broc, D.; Chaudat, T.; Feau, C.; Sollogoub, P.; Wang, F.; Baj, F.; Bung, H.; Combescure, D.; Lepareux, M.; Phalippou, C.; Bentejac, F.; Hourdequin, N.; Laporte, T.; Millard, A.; Nicolas, L.; Chapuliot, S.; Fissolo, A.; Gourdin, C.; Kayser, Y.; Marie, S.; Reytier, M.; Yuritzinn, T.; Magnaud, J.P. [CEA Saclay Dept. Modelisation de Systemes et Structures, 91 - Gif sur Yvette (France); Braillard, O.; Collard, B.; Gobillot, G.; Mori, V.; Vallory, J.; Pascal-Ribot, S.; Pluyette, E. [CEA Saclay, Dept. de Technologie Nucleaire, 91 - Gif sur Yvette (France); Berton, M.N.; Cabrillat, M.T.; Lejeail, Y. [CEA Saclay, Dept. d' Etudes des Reacteurs, 91 - Gif sur Yvette (France)


    The present report gives an overview of the ongoing research programmes in structural mechanics at CEA/DEN. On the whole, these contributions are well representative of the research work performed, more oriented by engineering concerns than driven by pure academic goals. Fundamentally, the developed knowledge results in new methods and improved engineering and computational tools that can be used for CEA needs and transferred to industrial clients and partners. Basic research is carried out with the help of university laboratories, what allows CEA teams to identify the underlying problems and to address them in an adequate manner. Confrontation with other viewpoints and backgrounds takes place in international cooperative actions conducted with academic or industrial research centres, often giving rise to benchmarks. Due to the wide range of problems submitted to CEA/DEN, the R and D topics are numerous and the effort devoted to each of them is limited and sometimes not continuous. Basic research is of course more limited and needs thorough preparation in order to ensure that the key questions, which lock the progress, are really addressed.. Before to end, it is worth mentioning two original research actions which have begun: -) identification of medium state and representation of its variability by a probabilistic approach: this original approach couples inverse method an probability to obtain non directly measurable value from global effect on structures (for example deduce damage from the displacement of a loaded beam) and should be applied to non destructive identification of present state of nuclear reactor enclosures, -) a program of numerical simulations of fluid-elastic instability of a tube bundle submitted to cross flow has been initiated with an Arbitrary Lagrangian Eulerian -ALE- finite element method to obtain a better knowledge and understanding of the phenomenon. From these simulations, the evolutions of pressure and velocity fields close to fluid

  8. Etude par imagerie radar des pollutions pétrolières

    Directory of Open Access Journals (Sweden)

    G. Rees


    Full Text Available En Russie, chaque année, les déversements de pétrole représentent un cinquième de la production totale. Les plus importants se produisent dans le domaine périglaciaire où le milieu naturel est d’une extrême fragilité. Les pipelines sont soumis à de rudes conditions notamment à la corrosion et aux processus cryogéniques. Le risque de rupture augmente en conséquence. La surveillance des déversements d’hydrocarbures, contrainte par l’immensité et la fréquente inaccessibilité du réseau de pipelines, peut être réalisée par le recours à la télédétection. L’objectif de ce travail est de fournir, à travers l’exemple de la catastrophe d’Usinsk (Rép. de Komi survenue en 1994, des outils d’analyse des images radar. Outre leur capacité à s’affranchir du couvert nuageux, les capteurs radar apportent des informations complémentaires à celles fournies par des capteurs optiques. L’exploitation thématique de ces images est rendue difficile par un certain nombre de facteurs perturbateurs tels que les caractéristiques propres du capteur, la direction de visée, la topographie et le phénomène de chatoiement (speckle. Le travail présenté montre le rôle prépondérant joué par ces corrections qui permettent de disposer de données quantitatives comparables d’une date à une autre. La méthode mise au point ici pour le suivi temporel de l’épanchement de pétrole d’Usinsk à partir de trois images radar, est discutée notamment dans ses limites et son aspect opérationnel possible.

  9. High Power Microwaves (HPM) (les Micro-ondes de forte puissance (MFP). (United States)


    B. Chevalier, D. Sirafin I)16gation Gdndrale pour r’Armement Direction des Recherches, Etudes et Techniques Centre dEtudes de Gramat 46500 Gramat ...MacMillan, New York, 1960. 4. Vargaftick, N. B., Handbook of Physical Properties of liquids and Gases, English Translation, published by Hemisphere...1993. - DGA/Direction des Recherches et Etudes Techniques [13] "G~n6rateur Pyrotechnique" J.P. Estienne, Compte - Centre d’Etude de Gramat Rendu de la

  10. Clinical and symptomatological study of pigs subjected to a lethal dose of integral gamma irradiation; Etude clinique et symptomatologique chez le porc soumis a une irradiation gamma totale a dose letale

    Energy Technology Data Exchange (ETDEWEB)

    Vaiman, M.; Guenet, J.-L.; Maas, J.; Nizza, P


    Results are reported from a clinical and haematological study on a Corsican species of pigs wholly exposed to an approximately lethal dose of {gamma} radiation. The aim of this work was to examine the changes in the irradiation syndrome of irradiation for pigs to make it thus possible to devise further experiments, in particular in the therapeutic field. The dose received was 285 rads (measured as the absorption in the vertical antero-posterior medial plane). Data are presented on cyto-haematological changes in the blood circulating immediately after irradiation, and followed up to death, and changes in the medullary cytology after irradiation. The clinical picture of lethal radiation injury in swine is described. (authors) [French] Les auteurs rapportent les resultats d'une etude clinique et hematologique chez des porcs de race corse irradies in toto a dose sensiblement letale. Le but de cette etude etait de connaitre l'evolution du syndrome aigu d'irradiation chez le porc et de permettre ainsi le developpement d'experimentations ulterieures, en particulier dans le domaine therapeutique. La dose delivree etait de 285 rad (en dose absorbee au niveau du plan median vertical anteroposterieur. L'etude a porte essentiellement: 1. Sur les modifications cyclo-hematologiques du sang circulant immediatement apres l'irradiation, pour les differentes lignees cellulaires; l'evolution de ces modifications a ete notee jusqu'a la mort; 2. Sur les modifications de la cytologie medullaire apres irradiation (evolution du myelogramme et essai d'evaluation de la cellularite de la moelle osseuse);: 3. Sur les signes cliniques, d'ailleurs tres discrets, observes chez les porcs apres irradiation. (auteurs)

  11. Experimental study of heat transfer and pressures drops for cans with spiral herring-bone fins; Etude experimentale du transfert de chaleur et des pertes de charges des gaines a ailettes helicoidales en chevron

    Energy Technology Data Exchange (ETDEWEB)

    Pelce, J.; Francois, S.; Houseaux, O.; Pierre, B. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires


    Cans fitted with herring-bone fins are used for cooling uranium in certain nuclear reactor. By herring-bone is meant a staggered arrangement of the fins which have a plane of symmetry parallel to the general direction of liquid flow. The main geometrical parameter are then: the number of fins, the number of herring-bones, the angle of inclination of the fins with respect to the can axis, the dimensions of the fins, the can diameter and the channel diameter. The research is essentially experimental. The test are of three types: full size tests, in conditions approaching those in the reactor (constant flux, CO{sub 2} under pressure); full size tests but with a constant wall temperature, much easier to set up, and intended to distinguish rapidly between the merits of the various types of can; large-scale tests with air at atmospheric pressure for studying the phenomena in more detail. For each can tried out there is a corresponding pressure drop coefficient, a mean thermal exchange coefficient Mo-bar and a minimum exchange coefficient Mo{sub min} and Mo-bar are related by the expression Mo{sub min} = Mo-bar * f{sub c} * f, where f{sub c} and f are respectively circumferential and longitudinal singularity factor determined from a statistical study of all the temperatures measured for each can. The results are presented in about thirty tables and figures the most noteworthy results being summarized in the conclusion. (authors) [French] Les gaines a ailettes en chevron sont utilisees pour le refroidissement de l'uranium dans certains reacteurs nucleaires. Par chevron, on entend une disposition alternee des ailettes ayant un plan de symetrie parallele a la direction generale de l'ecoulement fluide. Les principaux parametres geometriques sont alors: le nombre des ailettes, le nombre de chevrons, l'angle d'inclinaison des ailettes par rapport a l'axe de la gaine, les dimensions des ailettes, le diametre de la gaine et le diametre du canal. L'etude

  12. Study and installation of concrete shielding in the civil engineering of nuclear construction (1960); Etude et mise en place des betons de protection dans le genie civil des ouvrages nucleaires (1960)

    Energy Technology Data Exchange (ETDEWEB)

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


    The object of this report is to give technical information about high density concretes which have become very important for radiation biological shielding. The most generally used heavy aggregates (barytes, ilmenite, ferrophosphorus, limonite, magnetite and iron punching) to make these concretes are investigated from the point of view prospecting and physical and chemical characteristics. At first, a general survey of shielding concretes is made involving the study of components, mixing and placing methods, then, a detailed investigation of some high density concretes: barytes concrete, with incorporation of iron punching or iron shot, ferrophosphorus concrete, ilmenite concrete and magnetite concrete, more particularly with regard to grading and mix proportions and testing process. To put this survey in concrete form, two practical designs are described such as they have been carried out at the Saclay Nuclear Station. Specifications are given for diverse concretes and for making the proton-synchrotron 'Saturne' shielding blocks. (author) [French] Ce rapport a pour objet de donner des precisions techniques au sujet des betons a haute densite qui ont pris une grande importance pour la protection biologique contre les rayonnements. Les agregats lourds les plus couramment utilises (barytine, ilmenite, ferrophosphore, limonite, magnetite et riblons) pour la fabrication de ces betons, sont examines du point de vue prospection et caracteristiques physiques et chimiques. On procede d'abord a une etude generale des betons de protection comprenant l'etude des constituants, de la confection et de la mise en place, ensuite, a un examen detaille de quelques betons a haute densite: betons a base de barytine, avec incorporation de riblons ou de grenaille de fonte, betons au ferrophosphore, a base d'ilmenite ou de magnetite, notamment en ce qui concerne la granulometrie, la composition, le dosage et les processus d'essais. Pour concretiser ces

  13. Experimental study of contamination by inhalation of radioactive iodine aerosols. Biological balance; Etude experimentale de la contamination par inhalation d'aerosols d'iode radioactif bilan biologique

    Energy Technology Data Exchange (ETDEWEB)

    Marble, G. [Commissariat a l' Energie Atomique, 92 - Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires


    Several articles have been published concerning research into contamination produced by inhalation of radioactive iodine aerosols in monkeys. Results dealing with the biological balance of this contamination are presented and discussed in this report. (author) [French] L'etude experimentale de la contamination par inhalation d'aerosols d'iode radioactif effectuee chez le singe a fait l'objet de plusieurs publications. Les resultats concernant le bilan biologique de cette contamination sont presentes et discutes dans ce rapport. (auteur)

  14. Contribution to the study on the flow rate adjustment for gas cooled power reactors (1964); Contributiom a l'etude de reglage du debit pour les reacteurs industriels refroidis par gaz (1964)

    Energy Technology Data Exchange (ETDEWEB)

    Milliot, B. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires


    1. This original study firstly defines the problem of the adjustment of the coolant flow rate in a reactor channel as a function of the corresponding heat transfer equations and of the local and temporal neutron flux. The necessity of such an adjustment is pointed out and the modifying parameters are studied. An adjustment study using the envelope of the possible flux curves is developed. A short study on the technology and the economical advantage of this adjustment is presented. Some measurements, made on G-1 and G-2, show the precision one can obtain from adjustment apparatus itself as well as from the complete reactor adjustment system. 2. Evolution of nuclear properties of fuel in an heterogeneous thermal reactor. In the first port of this paper, the phenomena of fuel evolution have been mainly pointed out. Now a bibliographical study more qualitatively than quantitatively has been done. This survey specifies the present theories and relates to a real effective cross section and also yields to the bases of such a nuclear calculation. (author) [French] 1. Cette etude originale definit d'abord le probleme du reglage du debit de refrigerant dans un canal de reacteur en fonction de la formulation du calcul des performances thermodynamiques de ce canal et des variations du flux neutronique dans l'espace et le temps. La necessite du reglage est ensuite mise en evidence et les parametres le modifiant sont etudies. Une methode de reglage, basee sur l'emploi d 'une courbe enveloppe des courbes de flux possibles, est donnee. Une breve etude de la technologie et des incidences economiques du reglage est presentee. Des mesures effectuees sur les reacteurs G-1 et G-2 montrent la precision que l'on peut attendre des dispositifs de reglage comme du reglage d'ensemble du reacteur lui-meme. 2. Evolution des proprietes nucleaires du combustible dans un reacteur heterogene a neutrons thermiques. Les phenomenes d'evolution du combustible

  15. Etude des proprietes microstructurales et rheologiques de suspensions non-aqueuses d'argile (United States)

    Mobuchon, Christophe

    Phyllosilicates or layered silicates consist of individual layers with nanometric dimensions. In static fluids without external forces, attractive and repulsive colloidal forces acting between the colloidal layers lead to their self-organization on multiple length scales. Under flow, a wide range of complex rheological behaviors, including shear-thinning behavior and transition from fluid-like to solid-like behavior leading to thixotropic phenomena, is expected from structural evolution. Recently, layered silicates have attracted great interest as nanoscale fillers for reinforcement of polymers (PNCs) motivating the investigation of the structural properties of non-aqueous layered silicate suspensions. At the origin of this study, the linear and nonlinear viscoelastic properties of non-aqueous layered silicate suspensions were observed to depend on flow history. Hence, the ultimate aim of this work was to establish relationships between their rheological behavior and their structural properties. The picture of their inner structure has been achieved using a combination of light scattering techniques and advanced rheometric and microscopy measurements. The flow-induced orientation of the phyllosilicate has been quantified optically using linear dichroism measurements, and mechanically using a newly developed non-destructive method based on two-dimensional small amplitude oscillatory shear flow (2D-SAOS). The spatial distribution at the microscopic scale of the phyllosilicate has been inferred from small angle light scattering (SALS) patterns and directly observed using confocal laser microscopy (CLSM). The combination of these techniques allowed highlighting the microscopic and self-similar nature of non-aqueous phyllosilicate suspensions. The solid-like properties of these suspensions were consequently ascribed to the presence of space-filling networks made of mass fractal clusters. Under flow, the shear-thinning behavior of these suspensions was explained by the

  16. Physical activity patterns in the French 18-74-year-old population: French Nutrition and Health Survey (Etude Nationale Nutrition Santé, ENNS) 2006-2007. (United States)

    Salanave, Benoit; Vernay, Michel; Szego, Emmanuelle; Malon, Aurélie; Deschamps, Valérie; Hercberg, Serge; Castetbon, Katia


    To describe detailed physical activity and sedentary behaviour in French adults across physical activity categories. The French Nutrition and Health Survey (Etude Nationale Nutrition Santé, ENNS), conducted in 2006-2007, was a national cross-sectional survey based on three-stage random sampling. The International Physical Activity Questionnaire (IPAQ) was used to classify participants into three physical activity categories. Time spent in a sitting position and time spent in front of a screen were used as markers of sedentary behaviour. France. Adults (n 2971) aged 18 to 74 years were included. Overall, 29·5 % of men and 23·6 % of women were classified into the high-IPAQ category, while 36·1 % of men and 37·5 % of women were in the low-IPAQ category. For each intensity level of physical activity (vigorous intensity, moderate intensity or walking), the number of active days per week decreased from the high- to the low-IPAQ category and daily duration of physical activity was longer in the high-IPAQ category than in the other two categories; 6 % of adults declared neither vigorous nor moderate nor walking activities. For most adults in the low-IPAQ category, an increasing number of active days per week would be sufficient to attain the moderate-IPAQ category. This should be taken into account in public health initiatives aimed at promoting physical activity.

  17. Smoking Trajectories during the Perinatal Period and Their Risk Factors: The Nationally Representative French ELFE (Etude Longitudinale Française Depuis l'Enfance) Birth Cohort Study. (United States)

    El-Khoury, Fabienne; Sutter-Dallay, Anne-Laure; Van Der Waerden, Judith; Surkan, Pamela; Martins, Silvia; Keyes, Katherine; de Lauzon-Guillain, Blandine; Charles, Marie-Aline; Melchior, Maria


    In France, rates of perinatal smoking are among the highest worldwide; however, perinatal smoking trajectories and associated factors have still not been adequately researched. Among women participating in the French nationally representative etude longitudinale française depuis l'enfance birth cohort (n = 15,540), perinatal smoking trajectories were estimated using group-based modelling. Associated characteristics were studied using multinomial logistic regression. Four trajectories were identified: non-smokers (59%), quitters (20%), persistent moderate (12%) and persistent heavy (9%) smokers. Older age, being native French, low socioeconomic position, persistent psychological difficulties and alcohol use in pregnancy, lack of social support, partner's smoking, mistimed pregnancy, and child formula feeding at birth were associated with persistent heavy smoking. Most of these factors were also associated, but to a lesser extent, with persistent moderate smoking, except for age and migrant status, which had opposite effects. Women who successfully lost weight prior to pregnancy had higher levels of quitting smoking. Women's long-term smoking trajectories vary in terms of initial tobacco consumption level but also in relation to socio-demographic, psychological, behavioral and partner characteristics. Health professionals in contact with pregnant smokers should address perceived risks and benefits of smoking, including partner's smoking and weight-gain concerns. © 2017 S. Karger AG, Basel.

  18. A microcosm of musical expression. I. Quantitative analysis of pianists' timing in the initial measures of Chopin's Etude in E major. (United States)

    Repp, B H


    Patterns of expressive timing were measured in bars 1-5 of 115 commercially recorded performances of Chopin's Etude in E major, op. 10, No. 3. These patterns were subjected to principal components analysis, which suggested at least four independent "timing strategies": (1) major ritards at the ends of melodic gestures; (2) acceleration within some of these gestures, without final ritards; (3) extreme lengthening of the initial downbeat; and (4) ritards between as well as within melodic gestures. Strategies 1 and 4 respond in different ways to the melodic-rhythmic grouping structure of the music, and strategy 3 merely represents a local emphasis. Strategy 2 is the one most difficult to rationalize; it does not seem to represent an alternative structural interpretation of the music but rather an alternative gestural shaping. Each individual pianist's timing pattern could be described as a weighted combination of these four strategies plus idiosyncratic variation. A wide variety of combinations was represented, and no two individual patterns were exactly the same. In addition, there was a wide range of basic tempi and of degrees of tempo modulation. There were no strong relationships between any of these variables and sociocultural characteristics of the artists, although some weak trends were observed.

  19. A microcosm of musical expression. III. Contributions of timing and dynamics to the aesthetic impression of pianists' performances of the initial measures of Chopin's Etude in E major. (United States)

    Repp, B H


    Four judges repeatedly assessed the overall aesthetic quality of more than 100 recorded performances of the opening of Chopin's Etude in E major on a 10-point scale. The judgments, which exhibited reasonable reliability and modest intercorrelations, were entered into regression analyses with 16 independent variables derived from earlier objective analyses of the expressive timing and dynamics of the performances [Repp, J. Acoust. Soc. Am. 104, 1085-1100 (1998); 105, 1972-1988 (1999)]. Only between 9% and 18% of the variance in the judges' ratings was accounted for. By contrast, timing variables accounted for 53% of the variance in one judge's ratings of synthesized performances that varied in timing only and mimicked the timing patterns of the original performances. These results indicate, first, that the aesthetic impression of the original recordings rested primarily on aspects other than those measured (such as texture, tone, or aspects of timing and dynamics that eluded the earlier analyses) and, second, that very different patterns of timing and dynamics are aesthetically acceptable for the same music, provided that other, aesthetically more crucial performance aspects are present.

  20. A microcosm of musical expression: II. Quantitative analysis of pianists' dynamics in the initial measures of Chopin's Etude in E major. (United States)

    Repp, B H


    Patterns of expressive dynamics were measured in bars 1-5 of 115 commercially recorded performances of Chopin's Etude in E major, op. 10, No. 3. The grand average pattern (or dynamic profile) was representative of many performances and highly similar to the average dynamic profile of a group of advanced student performances, which suggests a widely shared central norm of expressive dynamics. The individual dynamic profiles were subjected to principal components analysis, which yielded Varimax-rotated components, each representing a different, nonstandard dynamic profile associated with a small subset of performances. Most performances had dynamic patterns resembling a mixture of several components, and no clustering of of performances into distinct groups was apparent. Some weak relationships of dynamic profiles with sociocultural variables were found, most notably a tendency of female pianists to exhibit a greater dynamic range in the melody. Within the melody, there were no significant relationships between expressive timing [Repp, J. Acoust. Soc. Am. 104, 1085-1100 (1998)] and expressive dynamics. These two important dimensions seemed to be controlled independently at this local level and thus offer the artist many degrees of freedom in giving a melody expressive shape.

  1. Electronic temperature measurement on the deca II plasma using the Bremsstrahlung; Mesure de la temperature electronique du plasma de deca II par etude du rayonnement de freinage

    Energy Technology Data Exchange (ETDEWEB)

    Dumas, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires


    The electronic temperature of the DECA II machine's plasma is determined by studying the Bremsstrahlung. Two types of detectors are used for this measurement, a set scintillator-photo-multiplicator and a photoelectric effect detector with a massive silver target. The method used is the classical 'absorbent method', The absorbents used are thin formvar foils whose thickness is between 600 and 12 500 angstrom. The measurements done in two different working conditions of the DECA II machine have given: Te {approx_equal} 200 eV in the first case and Te {approx_equal} 70 eV in the second case. (author) [French] Nous avons determine la temperature electronique du plasma de la machine DECA II par l'etude du rayonnement de freinage. Pour cette mesure nous avons utilise deux types de detecteurs: des ensembles scintillateur-photomultiplicateur et un detecteur a effet photoelectrique a cible massive en argent. La methode utilisee pour cette mesure est la classique methode des absorbants. Nous avons utilise des feuilles de format tres mince (de 600 a 12 500 angstrom) comme absorbant. Les mesures faites dans deux regimes de travail differents de la machine DECA II nous ont conduit a: Te {approx_equal} 200 eV dans un cas et Te {approx_equal} eV dans l'autre cas. (auteur)

  2. Etudes optiques de nouveaux materiaux laser: Des orthosilicates dopes a l'ytterbium: Le yttrium (lutetium,scandium) pentoxide de silicium (United States)

    Denoyer, Aurelie

    La decouverte et l'elaboration de nouveaux materiaux laser solides suscitent beaucoup d'interet parmi la communaute scientifique. En particulier les lasers dans la gamme de frequence du micron debouchent sur beaucoup d'applications, en telecommunication, en medecine, dans le domaine militaire, pour la, decoupe des metaux (lasers de puissance), en optique non lineaire (doublage de frequence, bistabilite optique). Le plus couramment utilise actuellement est le Nd:YAG dans cette famille de laser, mais des remplacants plus performants sont toujours recherches. Les lasers a base d'Yb3+ possedent beaucoup d'avantages compares aux lasers Nd3+ du fait de leur structure electronique simple et de leur deterioration moins rapide. Parmi les matrices cristallines pouvant accueillir l'ytterbium, les orthosilicates Yb:Y 2SiO5, Yb:Lu2SiO5 et Yb:Sc2SiO 5 se positionnent tres bien, du fait de leur bonne conductivite thermique et du fort eclatement de leur champ cristallin necessaire a l'elaboration de lasers quasi-3 niveaux. De plus l'etude fine et systematique des proprietes microscopiques de nouveaux materiaux s'avere toujours tres interessante du point de vue de la recherche fondamentale, c'est ainsi que de nouveaux modeles sont concus (par exemple pour le champ cristallin) ou que de nouvelles proprietes inhabituelles sont decouvertes, menant a de nouvelles applications. Ainsi d'autres materiaux dopes a l'ytterbium sont connus pour leurs proprietes de couplage electron-phonon, de couplage magnetique, d'emission cooperative ou encore de bistabilite optique, mais ces proprietes n'ont encore jamais ete mises en evidence dans Yb:Y 2SiO5, Yb:Lu2SiO5 et Yb:Sc2SiO 5. Ainsi, cette these a pour but l'etude des proprietes optiques et des interactions microscopiques dans Yb:Y2SiO 5, Yb:Lu2SiO5 et Yb:Sc2SiO5. Nous utilisons principalement les techniques d'absorption IR et de spectroscopie Raman pour determiner les excitations du champ cristallin et les modes de vibration dans le materiau

  3. Invariants of directed spaces

    DEFF Research Database (Denmark)

    Raussen, Martin


    Directed spaces are the objects of study within directed algebraic topology. They are characterised by spaces of directed paths associated to a source and a target, both elements of an underlying topological space. The algebraic topology of these path spaces and their connections are studied from...... a categorical perspective. In particular, we study the preorder category associated to a directed space and various "quotient" categories arising from algebraic topological functors. Furthermore, we propose and study a new notion of directed homotopy equivalence between directed spaces....

  4. Study and optimization of the ionisation channel in the Edelweiss dark matter direct detection experiment; Etude et optimisation de la voie ionisation dans l'experience Edelweiss de detection directe de la matiere noire

    Energy Technology Data Exchange (ETDEWEB)

    Censier, B


    The EDELWEISS experiment is aiming at the detection of Weakly Interactive Massive Particles (WIMPs), today's most favoured candidates for solving the dark matter issue. Background ionising particles are identified thanks to the simultaneous measurement of heat and ionisation in the detectors. The main limitation to this method is coming from the ionisation measurement, charge collection being less efficient in some part of the detectors known as 'dead' areas. The specificity of the measurement is due to the use of very low temperatures and low collection fields. This thesis is dedicated to the study of carrier trapping. It involves time-resolved charge measurements as well as a simulation code adapted to the specific physical conditions. We first present results concerning charge trapping at the free surfaces of the detectors. Our method allows to build a surface-charge in a controlled manner by irradiation with a strong radioactive source. This charge is then characterised with a weaker source which acts as a probe. In a second part of the work, bulk-trapping characteristics are deduced from charge collection efficiency measurements, and by an original method based on event localisation in the detector. The results show that a large proportion of the doping impurities are ionised, as indicated independently by the study of degradation by space-charge build-up. In this last part, near-electrodes areas are found to contain large densities of charged trapping centres, in connection with dead-layer effects. (author)

  5. Direct selling particularities


    Greifová, Daniela


    Bachelor thesis is focused on the parcularities of direct selling, self regulation of this industry, multi-level marketing which is the most used sales method in the field of direct selling. The part of the thesis is dedicated to the issue of customer psychology that is very important for achieving success in direct selling. Main goals are to provide readers with the general view of direct selling and analysis of growing possibilities of the industry in the future.

  6. Direct immunofluorescence microscopy

    NARCIS (Netherlands)

    Diercks, G.F.H.; Pas, Hendrikus; Jonkman, Marcel


    Direct immunofluorescence plays an important role in the diagnosis of autoimmune bullous diseases. The purpose of direct immunofluorescence microscopy is to detect in vivo antibodies in patient's skin or mucosa. Direct immunofluorescence of pemphigus shows depositions of immunoglobulins and/or

  7. A crystallographic and spectroscopic study of crystal sites in the 'spinel' structure; Etude cristallographique et spectroscopique des sites cristallins dans la structure 'spinelle'

    Energy Technology Data Exchange (ETDEWEB)

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


    A crystallographic study on magnesium aluminates led to the determination of crystal site average distortion. A spectroscopic study of transition elements doped spinels gave the position of the doping element in tetrahedral (A) or octahedral (B) sites, and the local distortion of the latter. The comparison of average and local parameters points to differences in the behaviour of doping elements and shows the size of (A) sites are independent of the host crystal composition while the average size of (B) sites varies with the composition. (author) [French] Une etude cristallographique des aluminates de magnesium a permis de determiner la deformation moyenne des sites cristallins. Une etude spectroscopique des aluminates de magnesium dopes avec des elements de transition a permis de localiser les dopants entre les sites tetraedriques (A) et octaedriques (B) et d'etudier la deformation locale de ces sites. La comparaison entre les parametres moyens et locaux a caracterise le comportement du dopant et montre que les dimensions des sites (A) sont independantes de la composition de la matrice, alors que les caracteristiques geometriques moyennes des sites (B) varient continument avec la composition. (auteur)

  8. Radio-vulcanization of natural rubber in the latex phase. Study of an experimental 1 tonne per hour production; Radio-vulcanisation du caoutchouc naturel en phase latex. Etude d'une production experimentale de 1 tonne par heure

    Energy Technology Data Exchange (ETDEWEB)

    Leveque, P.; Puig, J.R.; Roudeix, H. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires


    After briefly reviewing the main research carried out on the radio-vulcanization of latex and elastomers, a description is given of 4 types of cell which have been used successively with a view to industrial irradiation. They have made it possible to acquire the information necessary for resolving the main problem arising during irradiation - the formation of coagulum. The first two cell are designed for irradiation by a horizontal beam ('Dynamitron'), the two others use a vertical beam ('Circe'). The study of the properties of the rubber obtained shows it to compare favorably with 'Revultex'. In the appendix are given some characteristics of natural latex and information about its processing. (authors) [French] Apres un rappel des principales etudes sur la radio-vulcanisation du latex et des elastomeres, on decrit les quatre types de cellules successivement essayes en vue de l'irradiation industrielle. Ils ont permis d'acquerir les informations necessaires a la resolution du probleme principal pose par l'irradiation, la formation de coagulum au cours de celle,-ci. Les deux premiers sont concus pour l'irradiation par un faisceau horizontal ('Dynamitron'), les derniers par un faisceau vertical ('Circe'). L'etude des proprietes du caoutchouc obtenu montre qu'il se compare favorablement au 'Revultex'. Un apercu est donne en annexe des caracteristiques du latex naturel et de sa mise en oeuvre. (auteurs)

  9. Etude de la Dynamique de la Transition de Phase Ferroelectrique dans un Cristal de Potassium TANTALE(.93) NIOBIUM(.07) OXYGENE(3) a L'aide D'une Technique de Melange a Quatre Ondes Resolu dans le Temps (United States)

    Grenier, Paul

    Dans ce travail, nous presentons une etude de la dynamique de la transition de phase d'un echantillon de KTa_{.93}Nb_ {.07}O_3. Cette etude est basee principalement sur la mesure des caracteristiques de la branche polaritonique, associee au mode mou, en fonction de la temperature a l'aide d'une technique de melange a quatre ondes resolu dans le temps. De ces mesures, nous deduisons les caracteristiques du mode mou en fonction de la temperature, du vecteur d'onde et de la frequence. Les resultats obtenus pour la "self-energie" du mode mou dans la region du polariton presentent deux caracteristiques importantes. Premierement, la presence d'un pic a cq/n ~eq 1100 cm^{ -1} que nous interpretons comme etant du a une interaction anharmonique a quatre corps. Deuxiemement, la partie imaginaire de la "self-energie" s'avere etre plus elevee d'un facteur de l'ordre de deux que la valeur obtenue en diffusion Raman. L'interpretation la plus plausible relie cette difference a la presence de domaines ferroelectriques. De plus, l'evolution en temperature des tenseurs Raman et electro-optique, associee au mode mou, montre la predominance de ce dernier pres de T_{c}. Ces differents resultats abondent dans le sens d'un modele microscopique ou se sont les interactions electromagnetiques inter-i lots qui importent pour la dynamique des transitions de phase ferroelectrique dans ces systemes.

  10. [Acupuncture direction and analgesia]. (United States)

    Sun, Lu; Kou, Renzhong; Liu, Lanqing; Fan, Gangqi


    The acupuncture direction is closely related with the efficacy of acupuncture analgesia. In this article, the relationship between efficacy of acupuncture analgesia and factors, such as whether the needle towards disease location, whether the needle towards meridian direction, whether the needle following spinal cord direction and whether the needle following muscle direction, were analyzed. The previous clinical and literature research indicated that the needle towards disease location was superior to reverse direction, however, the efficacy of analgesia between needle following and reversing meridian, needle towards and at disease location, needles following and reversing spinal cord direction, needles following and reversing muscle direction was controversial. Therefore, the solutions to these problems will benefit the optimized acupuncture treatment plan for pain disorders.

  11. Characterization of core/shell Cu/Ag nanopowders synthesized by electrochemistry and assessment of their impact on hemolysis, platelet aggregation, and coagulation on human blood for potential wound dressing use (United States)

    Laloy, Julie; Haguet, Hélène; Alpan, Lutfiye; Mancier, Valérie; Mejia, Jorge; Levi, Samuel; Dogné, Jean-Michel; Lucas, Stéphane; Rousse, Céline; Fricoteaux, Patrick


    Copper/silver core/shell nanopowders with different metal ratio have been elaborated by electrochemistry (ultrasound-assisted electrolysis followed by a displacement reaction). Characterization was performed by several methods (X-ray diffraction, scanning electron microscope, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, centrifugal liquid sedimentation, and zeta potential measurements). The mean diameter of all nanoparticles is around 10 nm. The impact of each nanopowder on hemolysis, platelet aggregation, and coagulation has been studied on whole human blood. Hemolysis assays were performed with spectrophotometric measurement and platelet aggregation, with light transmission aggregometry and was compared to Cu/Pt core/shell nanoparticles with similar size as negative control. Calibrated thrombin generation test has been used for a coagulation study. They neither impact platelet aggregation nor hemolysis and have a procoagulant effect whatever their composition (i.e., metal ratio). These results highlight that such nanopowders have a potential use in medical applications (e.g., wound dressing).

  12. Direct electron transfer of hemoglobin in a CdS nanorods and Nafion composite film on carbon ionic liquid electrode

    International Nuclear Information System (INIS)

    Sun Wei; Wang Dandan; Li Guicun; Zhai Ziqin; Zhao Ruijun; Jiao Kui


    In this paper the direct electron transfer of hemoglobin (Hb) was carefully investigated by using a room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF 6 ) modified carbon paste electrode (CILE) as the basal working electrode. Hb was immobilized on the surface of CILE with the nanocomposite film composed of Nafion and CdS nanorods by a step-by-step method. UV-vis and FT-IR spectra showed that Hb in the composite film remained its native structure. The direct electrochemical behaviors of Hb in the composite film were further studied in a pH 7.0 phosphate buffer solution (PBS). A pair of well-defined and quasi-reversible cyclic voltammetric peaks of Hb was obtained with the formal potential (E 0 ') at -0.295 V (vs. SCE), which was the characteristic of heme Fe(III)/Fe(II) redox couples. The direct electrochemistry of Hb was achieved on the modified electrode and the apparent heterogeneous electron transfer rate constant (k s ) was calculated to be 0.291 s -1 . The formal potentials of Hb Fe(III)/Fe(II) couple shifted negatively with the increase of buffer pH and a slope value of -45.1 mV/pH was got, which indicated that one electron transfer accompanied with one proton transportation. The fabricated Hb sensor showed good electrocatalytic manner to the reduction of trichloroacetic acid (TCA)

  13. Xanthine oxidase/laponite nanoparticles immobilized on glassy carbon electrode: direct electron transfer and multielectrocatalysis. (United States)

    Shan, Dan; Wang, Yan-Na; Xue, Huai-Guo; Cosnier, Serge; Ding, Shou-Nian


    In this work, colloidal laponite nanoparticles were further expanded into the design of the third-generation biosensor. Direct electrochemistry of the complex molybdoenzyme xanthine oxidase (XnOx) immobilized on glassy carbon electrode (GCE) by laponite nanoparticles was investigated for the first time. XnOx/laponite thin film modified electrode showed only one pair of well defined and reversible cyclic voltammetric peaks attributed to XnOx-FAD cofactor at about -0.370 V vs. SCE (pH 5). The formal potential of XnOx-FAD/FADH(2) couple varied linearly with the increase of pH in the range of 4.0-8.0 with a slope of -54.3 mV pH(-1), which indicated that two-proton transfer was accompanied with two-electron transfer in the electrochemical reaction. More interestingly, the immobilized XnOx retained its biological activity well and displayed an excellent electrocatalytic performance to both the oxidation of xanthine and the reduction of nitrate. The electrocatalytic response showed a linear dependence on the xanthine concentration ranging from 3.9 x 10(-8) to 2.1 x 10(-5)M with a detection limit of 1.0 x 10(-8)M based on S/N=3.

  14. Descendants and advance directives. (United States)

    Buford, Christopher


    Some of the concerns that have been raised in connection to the use of advance directives are of the epistemic variety. Such concerns highlight the possibility that adhering to an advance directive may conflict with what the author of the directive actually wants (or would want) at the time of treatment. However, at least one objection to the employment of advance directives is metaphysical in nature. The objection to be discussed here, first formulated by Rebecca Dresser and labeled by Allen Buchanan as the slavery argument and David DeGrazia the someone else problem, aims to undermine the legitimacy of certain uses of advance directives by concluding that such uses rest upon an incorrect assumption about the identity over time of those ostensibly governed by the directives. There have been numerous attempts to respond to this objection. This paper aims to assess two strategies that have been pursued to cope with the problem.

  15. Contribution to the study of the sintering of finely divided alumina; Contribution a l'etude du frittage de l'alumine finement divisee

    Energy Technology Data Exchange (ETDEWEB)

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


    Two crystalline forms of alumina, delta and alpha, were used to prepare compacts. The shrinkage of these compacts was investigated at different temperatures. The samples of alumina are composed of non porous, spherical particles, of a very high purity. Their mean diameter varies between 160 and 1 200 Angstrom for the delta alumina samples and between 400 and 1 200 Angstrom for the alpha alumina samples. The shrinkage of compacts, heated at a linearly increasing temperature (300 deg. C/h, slow heating) was studied in a A.D.A.M.E.L. dilatometer, modified to be used as a retractometer. The kinetics of the isothermal shrinkage of compacts after their rapid introduction (a few seconds, flash heating) in the high temperature zone of the furnace were followed with a photographic technique. It is shown that the heating rate influences the shrinkage of the compacts when they are heated at temperatures over 1 000 deg. C. The kinetics of the isothermal shrinkage, at temperature between 1000 deg. C and 1600 deg. C were thoroughly studied. Values of the apparent activation energy for the different classes of compacts are given. An interpretation of the results is proposed. It takes into account two different but interdependent mechanisms of sintering: the disappearance of porosity as a result of vacancy diffusion and the grain growth as a result of boundary migration. (author) [French] Deux formes cristallines de l'alumine, la forme delta et la forme alpha, ont ete utilisees pour confectionner des comprimes en vue d'une etude cinetique du frittage. Ces alumines d'une tres grande purete sont constituees de particules spheriques non poreuses, sensiblement homodispersees dont le diametre moyen varie entre 160 et 1200 Angstrom pour les echantillons de l'alumine delta et entre 400 et 1200 Angstrom pour ceux de l'alumine alpha. Le retrait des comprimes chauffes a temperature linerairement croissante (300 deg. C/h: chauffage lent) a ete suivi a l'aide du

  16. Synthese, etude structurale et electrochimique des materiaux d'electrode positive d'oxydes mixtes lithium cobalt nickel oxide (0 /= 1) pour les batteries rechargeables au lithium (United States)

    Grincourt, Yves

    Depuis une dizaine d'annees, on observe un interet grandissant pour les batteries rechargeables au lithium de tension superieure a 4 volts. La commercialisation de ces batteries pour l'electronique grand marche tend de plus en plus a supplanter celle des accumulateurs Ni-Cd et Ni-MH, de tension nominate 1,2 V. Ces batteries au lithium font appel a des materiaux d'electrode positive (cathode a la decharge) du type oxydes mixtes de metaux de transition LiMnO 2, LiMn2O4, LiNiO2 ou LiCoO2. Si le compose LiCoO2 est relativement aise a synthetiser, il n'en demeure pas moins que le cobalt reste un metal plus couteux compare au nickel et au manganese. La synthese de LiNiO2, quart a elle, demeure un probleme du point de vue stoechiometrique. Un defaut de lithium (5 a 10% molaire) conduira a des proprietes electrochimiques mediocres de la batterie. Dans cette etude nous nous proposons donc de preparer par voie humide et par voie seche les materiaux d'electrode positive de la famille LiCoyNi1-yO2 aver (0 ≤ y ≤ 1) et d'etudier en detail l'influence du pourcentage de nickel et de cobalt sur les proprietes electrochimiques des oxydes mixtes Li-Ni-Co. Une des caracteristiques est la morphologie plus fine des poudres de materiaux, observes par microscopie electronique a balayage (MEB). Un traitement thermique a plus basse temperature (750°C) que pour LiCoO2 (850°C) ainsi qu'un leger exces de lithium dans la preparation, ont permis d'aboutir a un materiau de stoechiometrie quasi parfaite. Neanmoins, le role de pilfer joue par 2 a 4% de moles de Ni2+ presents sur les sites lithium, permet de conserver intacte la structure hexagonale de la maille entre deux cycles consecutifs. Afin de mieux comprendre l'influence du vieillissement dune demi-pile Li/LiMeO2 (Me = Ni, Co) a temperature ambiante, des etudes electrochimiques et d'impedance spectroscopique ont ete menees en parallele. Le vieillissement de la cellule s'accompagne seulement dune chute de son potentiel due a son auto

  17. Directional radiation detectors (United States)

    Dowell, Jonathan L.


    Directional radiation detectors and systems, methods, and computer-readable media for using directional radiation detectors to locate a radiation source are provided herein. A directional radiation detector includes a radiation sensor. A radiation attenuator partially surrounds the radiation sensor and defines an aperture through which incident radiation is received by the radiation sensor. The aperture is positioned such that when incident radiation is received directly through the aperture and by the radiation sensor, a source of the incident radiation is located within a solid angle defined by the aperture. The radiation sensor senses at least one of alpha particles, beta particles, gamma particles, or neutrons.

  18. Directed Energy Anechoic Chamber (United States)

    Federal Laboratory Consortium — The Directed Energy Anechoic Chamber comprises a power anechoic chamber and one transverse electromagnetic cell for characterizing radiofrequency (RF) responses of...

  19. Interleukin-6 gene polymorphisms and susceptibility to myocardial infarction: the ECTIM study. Etude Cas-Témoin de l'Infarctus du Myocarde. (United States)

    Georges, J L; Loukaci, V; Poirier, O; Evans, A; Luc, G; Arveiler, D; Ruidavets, J B; Cambien, F; Tiret, L


    There is growing evidence that interleukin (IL) 6 plays an important role in the atherosclerotic process because of its role in mediating immune and inflammatory responses and inducing cell proliferation. The present study examined whether molecular variations at the IL-6 locus are involved in the predisposition to myocardial infarction. The entire coding region, 1,158 bp of the 5' flanking region and 237 bp of the 3' flanking region of the IL-6 gene were screened. We detected three nucleotide substitutions in the 5' region at positions -174 (G/C), -572 (G/C), and -596 (G/A) from the transcription start site, and one insertion/deletion in the 3' region at position +528 after the Stop codon. These polymorphisms were genotyped in the Etude Cas-Témoin de l'Infarctus du Myocarde study comparing male patients (n=640) and age-matched controls (n=719) from Northern Ireland and France. The IL-6/G-174C and IL-6/G-596A polymorphisms were in nearly complete association. Carriers of the IL-6/-174 C allele were more frequent in patients than in controls. The population-adjusted odds ratio for myocardial infarction associated with genotype CC+CG vs. GG was estimated as 1.34. In French patients the number of coronary arteries with greater than 50% stenosis was assessed by angiography. The IL-6/-174 C allele was more frequent in patients with two or fewer stenosed vessels than in patients with three-vessel lesions. These results suggest that genetic variation at the IL-6 locus is associated with susceptibility to myocardial infarction, especially events occurring on less extended lesions. These findings would be compatible with a lower IL-6 secretion associated with the IL-6/-174 C allele, itself or in combination with other promoter polymorphisms, leading to more unstable plaques.

  20. Mise au point du rheometre a cisaillement annulaire pour l'etude de rheologie d'un mastic bitumineux avec verre incorpore = (United States)

    El Mansouri, Souleimane

    Dans le domaine viscoelastique lineaire (VEL, domaine des petites deformations), le comportement thermomecanique du bitume et du mastic bitumineux (melange uniforme de bitume et de fillers) a ete caracterise au Laboratoire des Chaussees et Materiaux Bitumineux (LCMB) de l'Ecole de technologie superieure (ETS) avec l'appui de nos partenaires externes : la Societe des Alcools du Quebec (SAQ) et Eco Entreprises Quebec (EEQ). Les proprietes rheologiques des bitumes et des mastics ont ete mesurees grâce a un nouvel outil d'investigation appele, Rheometre a Cisaillement Annulaire (RCA), sous differentes conditions de chargement. Cet appareil permet non seulement de solliciter des eprouvettes de tailles importantes par rapport a celles utilisees lors des essais classiques, mais aussi d'effectuer des essais en conditions quasi-homogenes, ce qui permet de donner acces a la loi de comportement des materiaux. Les essais sont realises sur une large gamme de temperatures et de frequences (de -15 °C a 45°C et de 0,03Hz a 10 Hz). Cette etude a ete menee principalement pour comparer le comportement d'un bitume avec celui d'un mastic bitumineux dans le domaine des petites deformations. neanmoins, dans une seconde perspective, on s'interesse a l'influence des fillers de verre de post-consommation sur le comportement d'un mastic a faibles niveaux de deformations en comparant l'evolution des modules complexes de cisaillements (G*) d'un mastic avec fillers de verre et un mastic avec fillers conventionnels (calcaire). Enfin, le modele analogique 2S2P1D est utilise pour simuler le comportement viscoelastique lineaire des bitumes et des mastics bitumineux testes lors de la campagne experimentale.

  1. Concerning the study of the irreversible magnetic behaviour of superconductivity; Contribution a l'etude du comportement magnetique irreversible des supraconducteurs

    Energy Technology Data Exchange (ETDEWEB)

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


    The influence of the presence of extended lattice defects on the magnetic behaviour has been studied for the case of type I superconductors, such as Re and Ta, and in a more quantitative manner for the type II superconductor niobium. In this case, measurements of the thermal conductivity have given an estimate of the relative concentration of lattice defects in each specimen. These measurements show that the larger the number of lattice defects, the more irreversible becomes the magnetization curve, and the larger becomes the values of the critical current, which is related by a simple model to the magnetization values. Finally, a study by transmission electron microscopy has confirmed on the one hand the diversity of the extended lattice defects and on the other hand has allowed the formulation of several hypothesis on their respective influence. [French] L'influence de la presence de defauts etendus sur le comportement magnetique a ete etudie pour des supraconducteurs de premiere espece, tels que le rhenium et le tantale, et plus quantitativement pour un supraconducteur de deuxieme espece, le niobium. Dans ce cas, des mesures de conductibilite thermique ont permis d'estimer la concentration relative des defauts du reseau dans chaque echantillon. Ces mesures montrent que plus les defauts du reseau sont nombreux, plus la courbe d'aimantation est irreversible, et plus les valeurs du courant critique, reliees par un modele simple aux valeurs de l'aimantation, sont elevees. Enfin une etude par microscopie electronique en transmission - a permis d'une part de constater la diversite des defauts etendus et d'autre part de formuler quelques hypotheses sur leurs influences respectives.

  2. Preliminary studies on the closed cycle magneto aerodynamic converter; Etudes preliminaires sur les convertisseurs magnetohydrodynamiques fonctionnant hors d'equilibre thermodynamique

    Energy Technology Data Exchange (ETDEWEB)

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


    electron heating in argon-potassium can be achieved by magnetic fields from 1 to 2 Ts. Plans are being made to build an important facility which will work on the principle of hot shots. The gas generator will deliver cesium-seeded helium shots at a temperature of 2100 deg. K. The shot will last 1/ 10 s and the instantaneous thermal power will reach 1 MW. (author) [French] A cote des convertisseurs magnetoaerodynamiques a cycle ouvert qui transforment l'energie thermique contenue dans les gaz de combustion on etudie tres attentivement le convertisseur a cycle ferme qui peut tirer son energie de toute source de chaleur a haute temperature et tout particulierement des sources nucleaires. Avant une etude pratique de l'ensemble de la centrale les performances du convertisseur lui-meme doivent etre bien delimitees. Ces performances sont largement fonction de la conductivite du gaz utilise. Mais cette conductivite ne doit pas etre payee par une temperature techniquement inadmissible pour l'echangeur de chaleur. Dans le fluide de conversion on est amene a associer un gaz porteur, helium ou argon, et une semence facilement ionisable cesium ou potassium. L'ionisation purement thermique n'est efficace qu'a partir de 2500 deg. K, par contre le champ electrique developpe par induction dans le convertisseur peut, sous certaines conditions, accroitre la temperature electronique et developper une ionisation bien superieure a la valeur d'equilibre. Il devient alors possible d'ioniser le gaz a temperature moderee. Des travaux en cours ont pour but de preciser les conditions permettant de creer cette ionisation hors d'equilibre dans les gaz rares ensemenses. Des mesures ont ete faites a l'aide d'un plasmatron triphase do 500 kVA alimente a l'argon ensemence de potassium. On a fait debiter cet appareil dans une cellule permettant de mesurer les composantes tensorielles de la conductivite en presence de champ magnetique. Les valeurs

  3. The Consumer Rights Directive

    NARCIS (Netherlands)

    Luzak, J.A.; Mak, V.; Hartkamp, A.S.; Sieburgh, C.H.; Keus, L.A.D.; Kortmann, J.S.; Wissink, M.H.


    This contribution discusses the impact of the CRD on Dutch private law. How will the new directive influence consumer rights and how does this fit with existing law? Considering the background of the directive and its importance for European consumer law, however, we discuss these questions in the

  4. Direct RF modulation transmitter

    NARCIS (Netherlands)

    Fukuda, Shuichi; Nauta, Bram


    PROBLEM TO BE SOLVED: To provide a direct RF modulation transmitter capable of saving more power consumption. SOLUTION: The direct RF modulation transmitter comprises: a passive mixer circuit 100 which inputs digital baseband data D of 1 bit, inverted data DN, a first RF signal, and a second RF

  5. Directionality effects in percolation (United States)

    Redner, Sidney

    The percolation properties of random networks containing resistors (two-way streets) and/or diodes (one-way streets) are considered. The directionality constraints of the diodes are found to lead to novel geometrical behavior. As a simple example, various random cluster models with a preferred direction, such as directed random walks or directed lattice animals, are shown to be anisotropic in character. The critical behavior of directed percolation is then treated and its connection with branching Markov processes is explained. A closely related "reverse" percolation problem, a transition from one-way percolation to isotropic percolation, is introduced. Finally, the geometrical properties of a network containing arbitrarily oriented diodes are treated. Symmetry and duality arguments are applied to yield exact results for certain aspects of its critical behavior.

  6. Study of the machining of uranium carbide rods obtained by continuous casting under electronic bombardment; Etude de l'usinage de barreaux de carbure d'uranium obtenus par coulee continue sous bombardement electronique

    Energy Technology Data Exchange (ETDEWEB)

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


    The authors consider the various methods of machining uranium mono-carbide and compare them critically in the case of their application to uranium carbide obtained by fusion under an electronic bombardment and continuous casting. This study leads them to propose two mechanical machining methods: cylindrical rectification and center-less rectification, preceded by a preliminary roughing out of a cylinder, the latter appearing more suitable. A study of the machining yields as a function of the diameter of the rough bars and of the diameter of the finished rods has shown that an optimum value of the rough bar diameter exists for each value of the finished rod diameter. It is found that the yield increases as the diameter itself increases, this yield rising from 45 per cent to around 70 per cent as the diameter of the rough bars increases from 25-26 mm to 37-38 mm. (authors) [French] Les auteurs envisagent les differentes methodes d'usinage du monocarbure d'uranium et se livrent a une etude critique de celles-ci, dans le cas de leur application a l'usinage de barreaux de carbure d'uranium obtenus par fusion sous bombardement electronique et coulee continue. Cette etude les conduit a proposer deux methodes d'usinage mecanique: la rectification cylindrique et la rectification 'centerless', precedee d'un ebauchage par carottage, la seconde paraissant la plus appropriee. L'etude des rendements d'usinage en fonction du diametre des barreaux bruts et du diametre des barreaux finis, a mis en evidence une valeur optimale du diametre des barreaux bruts pour chaque valeur du diametre des barreaux usines. Elle a montre que le rendement croit lorsque le diametre croit lui-meme, ce rendement passant d'environ 45 pour cent a environ 70 pour cent, lorsque le diametre des barreaux bruts passe de 25-26 mm a 37-38 mm.

  7. Direction of time

    International Nuclear Information System (INIS)

    Mirman, R.


    The meaning of the phrase ''the direction of time'' and the physical problems involved are considered. These problems are discussed, and plausibility arguments are given to show that all clocks run in the same direction (almost always), that the most probable development of the universe during the early stages of the expansion would result in the introduction of some internal organization, and that the expansion of the universe and the increase in entropy define time directions that have the same sense. The question of what properties of the laws governing the universe lead to these results is studied

  8. Abolition of Direct Payment for Health Services in West Africa | Page ...

    International Development Research Centre (IDRC) Digital Library (Canada)

    Agent(e) responsable du CRDI. Godt, Sue. Financement total. CAD$ 826,660. Pays. Afrique, Burkina Faso, Sud du Sahara, Mali, Niger. Chargé(e) de projet. OLIVIER de SARDAN, Jean Pierre. Institution. Laboratoire d'Etudes et de Recherches sur les Dynamyques Sociales et le Développement Local. Pays d' institution.

  9. A green non-acid-catalyzed process for direct N=N-C group formation: comprehensive study, modeling, and optimization. (United States)

    Khakyzadeh, Vahid; Zolfigol, Mohammad Ali; Derakhshan-Panah, Fatemeh; Jafarian, Majid; Miri, Mir Vahid; Gilandoust, Maryam


    The aim of this work is to introduce, model, and optimize a new non-acid-catalyzed system for a direct N[Formula: see text]N-C bond formation. By reacting naphthols or phenol with anilines in the presence of the sodium nitrite as nitrosonium ([Formula: see text] source and triethylammonium acetate (TEAA), a N[Formula: see text]N-C group can be formed in non-acid media. Modeling and optimization of the reaction conditions were investigated by response surface method. Sodium nitrite, TEAA, and water were chosen as variables, and reaction yield was also monitored. Analysis of variance indicates that a second-order polynomial model with F value of 35.7, a P value of 0.0001, and regression coefficient of 0.93 is able to predict the response. Based on the model, the optimum process conditions were introduced as 2.2 mmol sodium nitrite, 2.2 mL of TEAA, and 0.5 mL [Formula: see text] at room temperature. A quadratic (second-order) polynomial model, by analysis of variance, was able to predict the response for a direct N=N-C group formation. Predicted response values were in good agreement with the experimental values. Electrochemistry studies were done to introduce new Michael acceptor moieties. Broad scope, high yields, short reaction time, and mild conditions are some advantages of the presented method.

  10. Advance Directives - Multiple Languages (United States)

    ... Expand Section Advance Directives - 简体中文 (Chinese, Simplified (Mandarin dialect)) Bilingual PDF Health Information Translations Chinese, Traditional (Cantonese dialect) (繁體中文) Expand Section Advance ...

  11. Direct Conversion of Energy

    Energy Technology Data Exchange (ETDEWEB)

    Corliss, William R


    Topics include: direct versus dynamic energy conversion; laws governing energy conversion; thermoelectricity; thermionic conversion; magnetohydrodynamic conversion; chemical batteries; the fuel cell; solar cells; nuclear batteries; and advanced concepts including ferroelectric conversion and thermomagnetic conversion.

  12. Directed GF-spaces

    Directory of Open Access Journals (Sweden)

    F.G. Arenas


    Full Text Available In this paper we introduce the concept of directed fractal structure, which is a generalization of the concept of fractal structure (introduced by the authors. We study the relation with transitive quasiuniformities and inverse limits of posets. We define the concept of GF-compactification and apply it to prove that the Stone-Cech compactification can be obtained as the GF-compactification of the directed fractal structure associated to the Pervin quasi-uniformity.

  13. Synthesis and electrochemistry of β-pyrrole nitro-substituted cobalt(II) porphyrins. The effect of the NO₂ group on redox potentials, the electron transfer mechanism and catalytic reduction of molecular oxygen in acidic media. (United States)

    Sun, Bin; Ou, Zhongping; Yang, Shuibo; Meng, Deying; Lu, Guifen; Fang, Yuanyuan; Kadish, Karl M


    Four cobalt(II) porphyrins, two of which contain a β-pyrrole nitro substituent, were synthesized and characterized by electrochemistry and spectroelectrochemistry. The investigated compounds are represented as (TRPP)Co and (NO2TRPP)Co, where TRPP is the dianion of a substituted tetraphenylporphyrin and R is a CH3 or OCH3 substituent on the four phenyl rings of the macrocycle. Two reductions and three oxidations are observed for each compound in CH2Cl2 containing 0.10 M tetra-n-butylammonium perchlorate. The first reduction of the compounds without a nitro substituent is metal-centered and leads to formation of a Co(I) porphyrin which then reacts with the CH2Cl2 solvent to generate a carbon σ-bonded Co(III)-R complex. A further reduction then occurs at more negative potentials to generate an unstable Co(II) σ-bonded compound. In contrast to these reactions, the first reduction of the nitro-substituted porphyrins is macrocycle-centered under the same solution conditions and gives a Co(II) porphyrin π-anion radical product. This reversible electron transfer is then followed at more negative potentials by a second reversible one-electron addition to give a Co(II) dianion. Three reversible one-electron oxidations are also seen for each compound. The first is metal-centered and the next two involve the conjugated π-system of the macrocycle. Each neutral Co(II) porphyrin was also examined as to its catalytic activity for electroreduction of molecular oxygen when coated on an edge-plane pyrolytic graphite electrode in 1.0 M HClO4. The β-pyrrole nitro-substituted derivatives were shown to be better catalysts than the non-nitro substituted compounds under the utilized experimental conditions.

  14. Directional gear ratio transmissions (United States)

    Lafever, A. E. (Inventor)


    Epicyclic gear transmissions which transmit output at a gear ratio dependent only upon the input's direction are considered. A transmission housing envelops two epicyclic gear assemblies, and has shafts extending from it. One shaft is attached to a sun gear within the first epicyclic gear assembly. Planet gears are held symmetrically about the sun gear by a planet gear carrier and are in mesh with both the sun gear and a ring gear. Two unidirectional clutches restrict rotation of the first planet gear carrier and ring gear to one direction. A connecting shaft drives a second sun gear at the same speed and direction as the first planet gear carrier while a connecting portion drives a second planet gear carrier at the same speed and direction as the first ring gear. The transmission's output is then transmitted by the second ring gear to the second shaft. Input is transmitted at a higher gear ratio and lower speed for all inputs in the first direction than in the opposite direction.

  15. Re-entrant lithium local environments and defect driven electrochemistry of Li- and Mn-rich Li-ion battery cathodes. (United States)

    Dogan, Fulya; Long, Brandon R; Croy, Jason R; Gallagher, Kevin G; Iddir, Hakim; Russell, John T; Balasubramanian, Mahalingam; Key, Baris


    Direct observations of structure-electrochemical activity relationships continue to be a key challenge in secondary battery research. (6)Li magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can quantitatively characterize local lithium environments on the subnanometer scale that dominates the free energy for site occupation in lithium-ion (Li-ion) intercalation materials. In the present study, we use this local probe to gain new insights into the complex electrochemical behavior of activated 0.5(6)Li2MnO3·0.5(6)LiMn(0.5)Ni(0.5)O2, lithium- and manganese-rich transition-metal (TM) oxide intercalation electrodes. We show direct evidence of path-dependent lithium site occupation, correlated to structural reorganization of the metal oxide and the electrochemical hysteresis, during lithium insertion and extraction. We report new (6)Li resonances centered at ∼1600 ppm that are assigned to LiMn6-TM(tet) sites, specifically, a hyperfine shift related to a small fraction of re-entrant tetrahedral TMs (Mn(tet)), located above or below lithium layers, coordinated to LiMn6 units. The intensity of the TM layer lithium sites correlated with tetrahedral TMs loses intensity after cycling, indicating limited reversibility of TM migrations upon cycling. These findings reveal that defect sites, even in dilute concentrations, can have a profound effect on the overall electrochemical behavior.

  16. Graphene under direct compression: Stress effects and interlayer coupling

    Czech Academy of Sciences Publication Activity Database

    del Corro, Elena; Peňa-Álvarez, Miriam; Mračko, Michal; Kolman, Radek; Kalbáč, Martin; Kavan, Ladislav; Frank, Otakar


    Roč. 253, č. 12 (2016), s. 2336-2341 ISSN 0370-1972 R&D Projects: GA ČR GA14-15357S; GA MŠk LL1301 EU Projects: European Commission(XE) 696656 Institutional support: RVO:61388998 ; RVO:61388955 Keywords : graphene * high pressure * isotopic labeling * Raman spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 1.674, year: 2016

  17. Chromosomes and irradiation: in vitro study of the action of X-rays on human lymphocytes; Chromosomes et radiations: etude in vitro de l'action des rayons X sur les lymphocytes humains

    Energy Technology Data Exchange (ETDEWEB)

    Mouriquand, C.; Patet, J.; Gilly, C.; Wolff, C


    Radioinduced chromosomal aberrations were studied in vitro on leukocytes of human peripheral blood after x irradiation at 25, 50, 100, 200, and 300 R. The numeric and structural anomalies were examined on 600 karyotypes. The relationship between these disorders and the dose delivered to the blood are discussed. An explanation on their mechanism of formation is tentatively given. (authors) [French] L'etude in vitro des anomalies chromosomiques radioinduites a ete pratiquee sur des leucocytes de sang peripherique preleve chez 4 sujets et irradie aux doses de 25, 50, 100, 200, 300 R. Les aberrations numeriques et structurales ont ete examinees sur 600 caryotypes. Les rapports entre ces anomalies et les doses appliquees sont etudies. Une hypothese sur leur mecanisme de formation est avancee. (auteurs)

  18. Contribution to the study of plasmatic fibrinogen and serum albumin: effects of irradiation; Contribution a l'etude du fibrinogene et de la serum-albumine plasmatiques - effets de l'irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Suscillon, M. [Commissariat a l' Energie Atomique, Centre d' Etudes Nucleaires de Grenoble, 38 (France)


    The author studies the modifications of properties and structure of serum albumin and fibrinogen solution when subjected to radiation of low energy (X rays). On the other hand, two original techniques are exposed: 1. Amperometric determination of fibrin stabilizing factor or factor XIII of hemostasis. 2. Spectrophotometric study of fibrin formation kinetics. Then showing off and quantitative determination of platelets fibrinogen is exposed. (author) [French] L'auteur etudie les modifications des proprietes et de la structure des molecules de serum-albumine et de fibrinogene en solution soumise a un flux de RX de basse energie. D'autre part deux techniques originales sont exposees : 1. Dosage amperometrique du facteur stabilisant de la fibrine. 2. Etude spectrophotometrique de la cinetique de la fibro-formation. Enfin une mise en evidence et un dosage du fibrinogene plaquettaire sont presentes. (auteur)

  19. Directed network modules

    International Nuclear Information System (INIS)

    Palla, Gergely; Farkas, Illes J; Pollner, Peter; Derenyi, Imre; Vicsek, Tamas


    A search technique locating network modules, i.e. internally densely connected groups of nodes in directed networks is introduced by extending the clique percolation method originally proposed for undirected networks. After giving a suitable definition for directed modules we investigate their percolation transition in the Erdos-Renyi graph both analytically and numerically. We also analyse four real-world directed networks, including Google's own web-pages, an email network, a word association graph and the transcriptional regulatory network of the yeast Saccharomyces cerevisiae. The obtained directed modules are validated by additional information available for the nodes. We find that directed modules of real-world graphs inherently overlap and the investigated networks can be classified into two major groups in terms of the overlaps between the modules. Accordingly, in the word-association network and Google's web-pages, overlaps are likely to contain in-hubs, whereas the modules in the email and transcriptional regulatory network tend to overlap via out-hubs

  20. An in-situ surface electrochemistry approach toward whole-cell studies: Charge transfer between Geobacter sulfurreducens and electrified metal/electrolyte interfaces through linker molecules

    International Nuclear Information System (INIS)

    Kuzume, Akiyoshi; Zhumaev, Ulmas; Li, Jianfeng; Fu, Yongchun; Füeg, Michael; Esteve-Nuñez, Abraham; Wandlowski, Thomas


    Electrochemical reactivity and structure properties of electrogenic bacteria, Geobacter sulfurreducens (Gs) were studied to explore the heterogeneous electron transfer at the bacteria/electrode interface using electrochemical and in-situ spectroscopic techniques. The redox behavior of Gs adsorbed on a gold electrode, which is modified with a ω-functionalized self-assembled monolayer (SAM) of alkanethiols, depends strongly on the terminal group. The latter interacts directly with outermost cytochromes embedded into the outer membrane of the Gs cells. The redox potential of bacterial cells bound electrostatically to a carboxyl-terminated SAM is close to that observed for bacteria attached to a bare gold electrode, revealing a high electronic coupling at the cell/SAM interface. The redox potentials of bacterial cells adsorbed on amino- and pyridyl-terminated SAMs are significantly different suggesting that the outermost cytochromes changes their conformation upon adsorption on these SAMs. No redox activity of Gs was found with CH 3 -, N(CH 3 ) 3 + - and OH-terminated SAMs. Complementary in-situ spectroscopic studies on bacteria/SAMs/Au electrode assemblies were carried out to monitor structure changes of the bacterial cells upon polarization. Spectro-electrochemical techniques revealed the electrochemical turnover of the oxidized and reduced states of outer membrane cytochromes (OMCs) in Gs, providing evidence that the OMCs are responsible for the direct electron transfer to metal electrodes, such as gold or silver, during the electricity production. Furthermore, we observed spectroscopic signatures of the native structure of the OMCs and no conformational change during the oxidation/reduction process of the microorganisms. These findings indicate that the carboxyl-anchoring group provides biocompatible conditions for the outermost cytochromes of the Gs, which facilitate the heterogeneous electron transfer at the microorganism/electrode interface

  1. Experimental study of an ion cyclotron instability in a magnetic well confined plasma; Etude experimentale d'une instabilite cyclotronique ionique dans un plasma confine dans un puits magnetique

    Energy Technology Data Exchange (ETDEWEB)

    Brossier, P. [Commissariat a l' Energie Atomique, Fontenay-Aux-Roses (France). Centre d' Etudes Nucleaires


    This report is a contribution to the study of microinstabilities in macroscopically stable plasmas, in the low-{beta} limit. Ion cyclotron instabilities, with k{sub ||} = 0, have been numerically studied in detail; the computation of the density thresholds and growth rates of the different harmonics showed the relative role played by the following energy sources: density gradient, perpendicular distribution function and cold plasma component. This theoretical model has been compared with the results of a detailed study (density thresholds, wave structure, frequency spectrum, wavelengths, growth rate, amplitude of the electric field) of the instability observed in the DECA II device. This comparison gave a good agreement which shows the destabilising role played by the cold plasma component on a hot plasma with a loss cone distribution function. (author) [French] Ce rapport est une contribution a l'etude des microinstabilites dans les plasmas macroscopiquement stables, dans la limite des {beta} << 1. Les instabilites cyclotroniques ioniques, a k{sub ||} = 0, ont ete etudiees numeriquement en detail; le calcul des seuils de densite et taux de croissance des differents harmoniques a permis de preciser l'importance relative des facteurs destabilisants suivants: gradient de densite, fonction de distribution perpendiculaire, presence de plasma froid. Ce modele theorique a ete confronte avec les resultats d'une etude detaillee (seuils de densite, structure de l'onde, spectres de frequence, longueurs d'onde, taux de croissance, amplitude du champ electrique) de l'instabilite observee dans l'experience DECA II, Cette confrontation aboutit a un accord satisfaisant qui montre le role destabilisant joue par le plasma froid sur un plasma chaud presentant une distribution de cone de pertes. (auteur)

  2. X-spectrographic method for plutonium detection. Application to contamination measurements in humans; Etude d'une methode de detection du plutonium par spectrographie X. Application a la mesure des contaminations sur l'homme

    Energy Technology Data Exchange (ETDEWEB)

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


    After reviewing the radio-toxicology of plutonium 239 and conventional detection methods using its {alpha}-radiation, the author considers the measurement of the X emission spectrum of plutonium 239 using a proportional counter filled with argon under pressure. This preliminary work leads to the third part of this research involving the detailed study of the possibilities of applying thin alkali halide crystal scintillators to the detection of soft plutonium X-rays; there follows a systematic study of all the parameters liable to render the detection as sensitive as possible: movement due to the photomultiplier itself and its accessory electronic equipment, nature and size of the crystal scintillator as well as its mode of preparation, shielding against external parasitic radiation. Examples of some applications to the measurement of contamination in humans give an idea of the sensitivity of this method. (author) [French] Apres un apercu de la radiotoxicologie du plutonium 239 et des methodes classiques de detection par son rayonnement {alpha}, on etudie le spectre d'emission X du plutonium 239 avec un compteur proportionnel rempli avec de l'argon sous pression. Ce travail preliminaire permet d'aborder la troisieme partie de cette etude dans laquelle nous examinons d'une fagon approfondie les possibilites d'application des cristaux scintillateurs minces d'halogenure alcalin a la detection du rayonnement X mou du plutonium; suit une etude systematique de tous les parametres susceptibles de rendre la detection aussi sensible que possible: mouvement propre du photomultiplicateur et de l'electronique associee, nature et dimensions du cristal scintillateur ainsi que son mode de fabrication, blindage contre les rayonnements parasites exterieurs. Quelques applications a la mesure des contaminations sur l'homme permettent d'apprecier la sensibilite de cette methode. (auteur)

  3. Direct reading dosimeter

    International Nuclear Information System (INIS)

    Thomson, I.


    This invention is a direct reading dosimeter which is light, small enough to be worn on a person, and measures both dose rates and total dose. It is based on a semiconductor sensor. The gate threshold voltage change rather than absolute value is measured and displayed as a direct reading of the dose rate. This is effected by continuously switching the gate of an MOS transistor from positive to negative bias. The output can directly drive a digital readout or trigger an audible alarm. The sensor device can be a MOSFET, bipolar transistor, or MOSFET capacitor which has its electrical characteristics change due to the trapped charge in the insulating layer of the device


    Directory of Open Access Journals (Sweden)

    Izet Kahrović


    Full Text Available Hit directly, giving any impact maximum muscle strength is skill, and it is neces- sary to the exercise and learning to make it perfect. Training begins with oral statement, so that students get to know with the techni- que that works. After oral exposure, it is necessary to create a good notion on technology that is adopted. The best way for the creation of good notion is a good demonstration. In direct training kicks in the box, you need patience and gradualness and there- fore uses a large number of additional exercises. In their work with beginners, in the first class, individual elements of technology, and also direct blow, it is necessary to separate the parts and run them on multiple commands, to later come to the confluence in one command. Direct wounds, with left and right hand, can be run from the towns, on the head and body, from the movement, to step forward, step back and step aside, the remedy to the left and right side. Left direct is taking out from a running protrusion hands, but kick, which is a pro- duct of the system, ankle-knee-pelvis and shoulder forward horizontaly. Set at the time of stripes, body weight over the left leg. Right direct from the place, starting ekscentrical reflecsive impuls of a extensor muscle in ankle, knee and joint of a hip.This kind of a sud- den movement is running simultaneously with the rotation of the body around vertical (longitudinal axis, with the transfer body weight on the left leg. Further movement to the hand which serves as a lever, which is transmitted through the power stroke

  5. Directed flux motor (United States)

    Wilson, Andrew (Inventor); Punnoose, Andrew (Inventor); Strausser, Katherine (Inventor); Parikh, Neil (Inventor)


    A directed flux motor described utilizes the directed magnetic flux of at least one magnet through ferrous material to drive different planetary gear sets to achieve capabilities in six actuated shafts that are grouped three to a side of the motor. The flux motor also utilizes an interwoven magnet configuration which reduces the overall size of the motor. The motor allows for simple changes to modify the torque to speed ratio of the gearing contained within the motor as well as simple configurations for any number of output shafts up to six. The changes allow for improved manufacturability and reliability within the design.

  6. Direct subdural scintigraphy

    Energy Technology Data Exchange (ETDEWEB)

    Keren, G.; Barzilay, Z.; Czerniak, P.; Cohen, B.E.


    We report a case of pneumococcal meningitis in an 8 weeks old female infant followed by persistent subdural effusion successsfully treated by repeated subdural taps. The initial delineation of the subdural effusion, the decrease in size and the disappearance of the fluid were demonstrated by direct subdural scintigraphy (D.S.S.). The literature of pneumoccocal meningitis, its diagnosis, treatment and complications are reviewed, and it is suggested that direct subdural scintigraphy should be employed as a diagnostic aid in the evaluation and follow up of subdural effusions.

  7. Handedness of direct photons

    International Nuclear Information System (INIS)

    Kopeliovich, B.Z.; Rezaeian, A.H.; Schmidt, Ivan


    The azimuthal asymmetry of direct photons originating from primary hard scatterings between partons is calculated. This can be accounted for by the inclusion of the color dipole orientation, which is sensitive to the rapid variation of the nuclear profile. To this end we introduce the dipole orientation within the saturation model of Golec-Biernat and Wuesthoff, while preserving all its features at the cross-section level. We show that the direct photon elliptic anisotropy v2 coming from this mechanism changes sign and becomes negative for peripheral collisions, albeit it is quite small for nuclear collisions at the RHIC energy. (author)

  8. The direction of time

    CERN Document Server

    Reichenbach, Hans


    Ever a source of philosophical conjecture and debate, the concept of time represents the beating heart of physics. This final work by the distinguished physicist Hans Reichenbach represents the culmination and integration of a lifetime's philosophical contributions and inquiries into the analysis of time. The result is an outstanding overview of such qualitative, or topological, attributes of time as order and direction.Beginning with a discussion of the emotive significance of time, Reichenbach turns to an examination of the time order of mechanics, the time direction of thermodynamics and m

  9. Etude de la distribution des champs magnetostatiques dans une section d'essais de type CANDU chauffee par effet de joule (United States)

    Hall, Darren

    Parmi tous les parametres physiques consideres lors de l'analyse de surete d'un reacteur nucleaire, le flux de chaleur critique (FCC) fait partie des plus importants. Afin d'etudier le FCC sous des conditions experimentales relativement securitaires, la chaleur degagee par le combustible nucleaire peut etre reproduite grâce a l'effetet de Joule. Or, afin de generer la puissance thermique necessaire pour les experiences sur le FCC des reacteurs CANDU, des courants electriques tres eleves de l'ordre de plusieurs dizaines de milliers d'amperes sont requis ce qui genere un champ magnetostatique tres intense capable d'interagir avec la section d'essais et l'instrumentation. Consequemment, l'industrie nucleaire est preoccupee par les effets de ce champ magnetique sur les donnees collectees et par les forces d'origine magnetique agissant sur le systeme. Dans ce contexte, le travail presente dans ce memoire de maitrise vise l'implementation d'une methodologie de calcul capable de fournir une information detaillee sur le champ magnetique engendre par ces courants. Toutefois, etant donne la complexitee du systeme, une etude magnetostatique appropriee requiert une methode numerique afin d'obtenir une distribution fiable du champ magnetique a travers differentes structures de la section d'essais. a cet effet, nous considerons dans le cadre de ce memoire le volume integral equation method (VIEM), une methode bien etablie basee sur les solutions integrales des equations de Maxwell. Plus precisement, nous employons le VIEM afin d'etudier la distribution du champ magetique a l'interieur de la section d'essais et pour determiner l'influence des prises concues pour le branchement des capteurs de pression sur la symetrie de cette distribution. Etant donne que les methodes integrales incluent les conditions aux limites et par consequent ne requierent pas l'emploi d'un critere de convergence, nous proposons une nouvelle technique de discretisation. L'emploi de cette procedure nous

  10. Data processing in gamma spectrometry. Application to the decay schemes study; Traitement des informations en spectrometrie gamma application a l'etude de schemas de desintegration

    Energy Technology Data Exchange (ETDEWEB)

    Boulanger, J.P. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires, departement d' electronique generale, service d' instrumentation nucleaire


    The purpose of this thesis is the processing of the data issued from a gamma spectrometer, and its applications to the decay schemes study. The mathematical analysis of the full energy peaks, in connection with the very good resolution of semi-conductor detectors, leads to a very accurate determination of the energies. The resolution of complex spectra by the least squares method, completed by a spectra generating process, allows the calculation of branching ratios. Then, the handling of the two dimensional experiments permits the coincidence exam. For each of these methods, the calculation principle, then the systematics tests realized in order to prove their validity and to determine their application ranges as well as some experimental results appropriate to illustrate their possibilities, are presented. The energies of some nuclides, frequently used as standards have been thus measured and the decay schemes of {sup 134}Cs and {sup 110m}Ag determined precisely. (author) [French] Cette these est consacree aux methodes de traitement des informations issues d'un spectrometre {gamma}, et a leur application a l'etude des schemas de desintegration: l'analyse mathematique des pics d'absorption totale, conjuguee avec l'excellent pouvoir de resolution des detecteurs semi-conducteurs, conduit a une determination tres precise des energies. La decomposition des spectres complexes par la methode des moindres carres, completee par un procede de generation de spectres, autorise le calcul des rapports de branchement. Enfin le depouillement des experiences biparametriques permet l'examen des coincidences. Pour chacune de ces methodes, on expose le principe des calculs et les essais systematiques effectues afin d'eprouver leur validite et de definir leurs domaines d'application, ainsi que quelques resultats experimentaux propres a illustrer leurs possibilites. Les energies de quelques isotopes utilises couramment comme etalons ont ainsi ete

  11. Study of various processes for marking sediments with gold-198; Etude de divers procedes de marquages de sediments par l'or 198

    Energy Technology Data Exchange (ETDEWEB)

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


    The use of radioactive isotopes for the study of sediment deposits is based mainly on two methods: marking in the mass - a glass of an element which can be activated replaces the sediment; surface marking - a physico-chemical process is used to deposit a radio-element at the surface of the sediment. The second process is used in particular for sands when it is advantageous to have a large number of particles for statistical analysis. The aim of this work was to develop a rapid and simple method of marking which could be applied on the actual site of the experiment where equipment, may be limited. The method recommended for marking sand with gold-198 is a combination of the Petersen (treatment with tin chloride) and Campbell (treatment with silver) methods combined with prior treatments with nitric acid and caustic soda. Using this method it is possible to deposit 125 mg of gold per kilo of sediment with a yield of 95 per cent (i.e. 10 Ci/kg) using a hydrochloric acid solution containing gold. The problem of the solidity of the deposits, of their value and of their reproducibility is discussed from the point of view of the mineral constitution of the sand. (author) [French] L'utilisation d'isotopes radioactifs pour l'etude des deplacements sedimentaires fait, principalement appel a deux methodes: le marquage massique - un verre contenant un element activable remplace le sediment; le marquage superficiel - un traitement physico-chimique permet de deposer un radioelement a la surface du sediment. Le second procede est surtout employe pour les sables lorsqu'il est utile de disposer d'un grand nombre de grains pour des raisons statistiques. Le but de ce travail etait de mettre au point une methode simple et rapide de marquage pouvant etre appliquee sur le site meme de l'experience pour les utilisateurs disposant d'un equipement limite. Le procede preconise pour le marquage des sables par l'or 198 est une combinaison des methodes

  12. Preliminary studies leading to a conceptual design of a 1000 MWe fast neutron reactor; Etudes preliminaires conduisant a un concept de reacteur a neutrons rapides de 1000 MWe

    Energy Technology Data Exchange (ETDEWEB)

    Vendryes, G.; Zaleski, C.P. [Association Euratom-CEA Cadarache (France). Centre d' Etudes Nucleaires


    This report presents the results of studies which seemed important to undertake in connexion with the development of fast neutron reactors. - It points out the advantage of high internal breeding ratios ({approx}1, 1) which are necessary in order to get a small change in time both in power distribution and reactivity (less: than 0.005 {delta}k/k in 18 months). - It shows how to achieve this goal, when simultaneously power distribution flattening is obtained. These results in a higher mean specific power (which is an economic gain) and therefore in a smaller doubling time (about 10 years). - It attempts to find criteria concerning the specific power that should be used in future reactor designs -It presents a conceptional design of a 1000 MWe fast neutron reactor, for the realisation of which no technological impossibility appears. - It shows that the dynamic behaviour seems satisfactory despite a positive total isothermal sodium coefficient. - It tries to predict the development of fast reactors within the future total nuclear program. It does not appear that fissile materials supply problems should in France slow down the development of fast neutron reactors, which will be essentially tied up to its economical ability to produce cheap electric power. (authors) [French] Ce rapport presente les etudes qu'il nous a paru important d'aborder dans le cadre du developpement des reacteurs a neutrons rapides. - Il met en evidence l'interet des taux de regeneration internes eleves ({approx}1, 1) pour obtenir une bonne evolution dans le temps de la distribution de puissance et de la reactivite (moins de 0,005 {delta}k/k pour 18 mois). - Il montre la possibilite d'y parvenir tout en applatissant la distribution des fissions, ce qui se traduit par une puissance specifique moyenne plus elevee (gain economique), et donc un temps de doublement plus faible de l'ordte de 10 ans - Il tente de definir un optimum de la puissance specifique valable pour les

  13. Polymer Directed Protein Assemblies

    Directory of Open Access Journals (Sweden)

    Patrick van Rijn


    Full Text Available Protein aggregation and protein self-assembly is an important occurrence in natural systems, and is in some form or other dictated by biopolymers. Very obvious influences of biopolymers on protein assemblies are, e.g., virus particles. Viruses are a multi-protein assembly of which the morphology is dictated by poly-nucleotides namely RNA or DNA. This “biopolymer” directs the proteins and imposes limitations on the structure like the length or diameter of the particle. Not only do these bionanoparticles use polymer-directed self-assembly, also processes like amyloid formation are in a way a result of directed protein assembly by partial unfolded/misfolded biopolymers namely, polypeptides. The combination of proteins and synthetic polymers, inspired by the natural processes, are therefore regarded as a highly promising area of research. Directed protein assembly is versatile with respect to the possible interactions which brings together the protein and polymer, e.g., electrostatic, v.d. Waals forces or covalent conjugation, and possible combinations are numerous due to the large amounts of different polymers and proteins available. The protein-polymer interacting behavior and overall morphology is envisioned to aid in clarifying protein-protein interactions and are thought to entail some interesting new functions and properties which will ultimately lead to novel bio-hybrid materials.

  14. Direct vision internal urethrotomy

    DEFF Research Database (Denmark)

    Jakobsen, H; Willumsen, H; Søndergaard Jensen, L


    During a five-year period, direct vision internal urethrotomy was used for the treatment of urethral strictures in 34 men. After the primary operation the patients were followed for an average period of 29 months (range 3-73 months). During this period 53% of the patients were found to have one...

  15. CGH Future Directions (United States)

    Looking ahead, we have three major future directions that we believe will help us push forward in achieving NCI’s goal of advancing global cancer research, building expertise, and leveraging resources across nations to address the challenges of cancer and reduce cancer deaths worldwide.

  16. Summary and future directions (United States)

    Janaki R.R. Alavalapati; D. Evan Mercer


    This chapter summarizes the main results from the preceding chapters, identifies gaps, and provides direction for fbture economics research on agroforestry systems. Although a common theme throughout the 1990s was that economic research on agroforestry continued to lag the advances made in the bio-physical sciences, the wide range of systems, regions, and techniques...

  17. Directional loudness perception

    DEFF Research Database (Denmark)

    Sivonen, Ville Pekka

    developed. The research and modeling of loudness have mainly been concerned with the temporal and spectral aspects of sounds, while the spatial aspects have mostly been overlooked. This PhD thesis investigates the spatial aspects of loudness perception, namely, how does the direction from which a sound...

  18. Direct Sulfation of Limestone

    DEFF Research Database (Denmark)

    Hu, Guilin; Dam-Johansen, Kim; Wedel, Stig


    The direct sulfation of limestone was studied in a laboratory fixed-bed reactor. It is found that the direct sulfation of limestone involves nucleation and crystal grain growth of the solid product (anhydrite). At 823 K and at low-conversions (less than about 0.5 %), the influences of SO2, O-2...... and CO2 on the direct sulfation of limestone corresponds to apparent reaction orders of about 0.2, 0.2 and -0.5, respectively. Water is observed to promote the sulfation reaction and increase the apparent reaction orders of SO2 and O-2. The influence of O-2 at high O-2 concentrations (> about 15...... %) becomes negligible. In the temperature interval from 723 K to 973 K, an apparent activation energy of about 104 kJ/mol is observed for the direct sulfation of limestone. At low temperatures and low conversions, the sulfation process is most likely under mixed control by chemical reaction and solid...

  19. Direct contamination - seasonality

    International Nuclear Information System (INIS)

    Aarkrog, A.


    Direct contamination is the primary pathway to terrestrial vegetation in the first period after an activity release to the atmosphere. All radionuclides are able to be transferred via this pathway. Deposition, interception and retention are the three processes involved in direct contamination of crops. Wet deposition is more important than dry deposition in temperature regions. Resuspension and rainsplash both belong to secondary direct deposition and became evident for e.g. radiocaesium after the Chernobyl accident. Seasonality is the varying response to radioactive contamination of crops according to the time of the year when the contamination occurs. Shortlived radionuclides (as 131 I) and those that mainly enter the foodchain by direct contamination (e.g. 137 Cs) are especially important in this connection. In particular, the contamination of cereal crops is influenced by seasonality. As a result of seasonality the impact of the Chernobyl accident on the radioactive contamination of human diet was for the same deposition density higher in southern than in northern Europe. (orig.)

  20. Direct fired heat exchanger (United States)

    Reimann, Robert C.; Root, Richard A.


    A gas-to-liquid heat exchanger system which transfers heat from a gas, generally the combustion gas of a direct-fired generator of an absorption machine, to a liquid, generally an absorbent solution. The heat exchanger system is in a counterflow fluid arrangement which creates a more efficient heat transfer.

  1. Direction des Publications

    African Journals Online (AJOL)


    Experimental research of fluid flow and convection heat transfer in plate channels filled with glass or metallic particles, Experimental Thermal and Fluid. Science, Vol.20, Issue.1, 45-54. [7] Rahimian M.H., Pourshaghaghy A.,. 2002. Direct simulation of forced convection flow in a parallel plate channel filled with porous media, ...

  2. Advanced directives: open issues

    Directory of Open Access Journals (Sweden)

    Gabriella Negrini


    Full Text Available BACKGROUND In Italy Advanced directives have not been regulated by law yet. Moreover, there is a confusion of concepts: advanced directives, refusal of treatment, medical futility and euthanasia are not synonymous.DISCUSSION The following aspects are then discussed: object of directives; elapse of time between their expression and their application; knowledge of the directives and their obligatory nature. The refusal of a treatment that can save a person’s life is a critical subject. There are different ethical points of view: according to lay ethics, the patient’s self-determination prevails; the religious viewpoint, instead, says that life is a gift which we cannot dispose of. In any case, the patient will be confronted with the professional autonomy of the doctor. Should the doctor save a patient’s life in any case or should he achieve best clinical practice, in respect of his will? The doctor should interpret the patient’s will but with caution and judgment. An exemption from responsibility should be provided by law for doctors who respect patient’s living will.

  3. The Directed Case Method. (United States)

    Cliff, William H.; Curtin, Leslie Nesbitt


    Provides an example of a directed case on human anatomy and physiology. Uses brief real life newspaper articles and clinical descriptions of medical reference texts to describe an actual, fictitious, or composite event. Includes interrelated human anatomy and physiology topics in the scenario. (YDS)

  4. Copper corrosion in irradiated environments. The influence of H2O2 on the electrochemistry of copper dissolution in HC1 electrolyte

    International Nuclear Information System (INIS)

    Smyrl, W.H.; Bell, B.T.; Atanasoski, R.T.; Glass, R.S.


    The anodic dissolution of copper has been examined in deaerated, 0.1 M HCl aqueous solution in the presence of H 2 O 2 . Concentrations of H 2 O 2 up to 0.2 M were studied at a rotating copper disk-platinum ring electrode. The open circuit potential (OCP) of copper was found to depend on both peroxide concentration and rotation rate. The OCP shifts towards more positive values with increasing H 2 O 2 concentration (C) and decreasing rotation rate (Omega). The dependence of OCP on (C/Omega/sup 1/2/) was the same as for oxygenated solutions reported earlier [1], at small values of (C/Omega/sup 1/2/). At higher values of (C/Omega/sup 1/2/), departure from the expected behavior was observed. The current-voltage curves for anodic dissolution of copper were also influenced by the presence of peroxide. The curves recorded with the potential scanned in the positive direction showed the expected 60 mV slope, but the reverse scans showed significant departures. At a given potential scan rate, hysteresis was observed which was larger for higher H 2 O 2 concentrations, lower rotation rates, and more positive anodic potential limits. Monitoring the cuprous ions at the outer Pt ring revealed that there was a complex set of events taking place at the copper surface, including film formation and the appearance of cupric ions. 13 references, 7 figures

  5. CO{sub 2} direct cycles suitable for AGR type reactors; Cycles directs de gaz carbonique applicables aux reacteurs du genre AGR

    Energy Technology Data Exchange (ETDEWEB)

    Maillet, E. [Commissariat a l' Energie Atomique. Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France)


    The perspectives given by the gas turbines under pressure, to build simple nuclear power plants and acieving significantly high yield, are specified. The CO{sub 2} is characterised by by good efficiency under moderate temperature (500 to 750 Celsius degrees), compactness and the simpleness of machines and the safe exploitation (supply, storage, relief cooling, thermosyphon). The revision of thermal properties of the CO{sub 2} and loss elements show that several direct cycles would fit in particular to the AGR type reactors. Cycles that would diverge a little from classical models and able to lead to power and heat generation can lead by simple means to the best results. Several satisfying solutions present for the starting up, the power regulation and the stopping. The nuclear power plant components and the functioning safety are equally considered in the present report. The conclusions stimulate the studies and realizations of carbon dioxide gas turbines in when approprite. [French] Les perspectives offertes par la turbine a gaz sous pression, pour construire des centrales nucleaires simples et de rendement progressivement eleve, se precisent actuellement. le CO{sub 2} se distingue par sa bonne efficacite a temperature moderee (500 a 750 degres celsius), la compacite et la simplicite des machines, et la surete qu'il apporte a l'exploitation ( approvisionnement, stockage, refroidissement de secours, thermosiphon). La revision des proprietes thermophysiques du CO{sub 2} et des elements de pertes montre que divers cycles directs conviendraient en particulier aux reacteurs agr ou derives. Des cycles s'ecartant peu des modeles classiques, et se pretant ulterieurement a la production simultanee d'electricite et de chaleur, peuvent conduire par des moyens simples aux meilleurs resultats d'ensemble. Plusieurs solutions satisfaisantes se presentent pour le demarrage, le reglage de la puissance et l'arret. Les composants de la centrale et la

  6. Les activités de conservation des lémuriens par le Groupe d’Etude et de Recherche sur les Primates de Madagascar (GERP Conservation activities of lemurs by the Madagascar Primate Research Group (GERP- Groupe d’Etude et de Recherche sur les Primates de Madagascar

    Directory of Open Access Journals (Sweden)

    Rose Marie Randrianarison


    Full Text Available Le Groupe d’Etude et de Recherche sur les Primates de Madagascar, une association de conservation, a été créée en 1994 grâce à l’initiative des Enseignants Chercheurs et étudiants du Département de Paléontologie et d’Anthropologie Biologique et du Département de Biologie Animale de l’Université d’Antananarivo. Le GERP regroupe actuellement des membres scientifiques multidisciplinaires Malgaches et étrangers dont la majorité d’entre eux est constituée par des primatologues. Les principales actions du GERP se focalisent sur les travaux de recherche sur les Primates Prosimiens de Madagascar, l’établissement de leur plan de conservation, la découverte de nouvelles espèces de lémuriens, la translocation et le transfert des lémuriens vivant dans des milieux défrichés ou précaires, le suivi et l’abondance des lémuriens ainsi que la révision de leurs aires de distribution. Les résultats des recherches effectuées sur la conservation ont permis de publier des articles dans des revues de renommée nationale et internationale sur la Primatologie. En outre, le renforcement de capacité et l’éducation de la communauté de base, des systèmes éducatifs primaires et supérieurs sur la conservation des lémuriens et l’appui aux activités de développement durable de la population locale s’avèrent nécessaires pour que la conservation des lémuriens soit pérenne.The Madagascar Primate Research Group (GERP - Groupe d’Etude et de Recherche sur les Primates de Madagascar is a conservation-focused association created in 1994 by the initiative of researcher lecturers and students from the Department of Paleontology and Biological Anthropology and the Department of Animal Biology of the University of Antananarivo. The GERP membership consists of multidisciplinary scientists, both Malagasy and foreign, the majority of whom are primatologists. The principle actions of the association are focused on research on the

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

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


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

  8. Comparison of Dietary Intakes Between a Large Online Cohort Study (Etude NutriNet-Santé) and a Nationally Representative Cross-Sectional Study (Etude Nationale Nutrition Santé) in France: Addressing the Issue of Generalizability in E-Epidemiology. (United States)

    Andreeva, Valentina A; Deschamps, Valérie; Salanave, Benoît; Castetbon, Katia; Verdot, Charlotte; Kesse-Guyot, Emmanuelle; Hercberg, Serge


    Despite some advantages over traditional methods, Web-based studies elicit concerns about generalizability. To address this issue, we compared dietary intakes between an electronic (e-) cohort study and a nationally representative survey. We studied 49,443 French volunteers aged 18-74 years recruited during 2009-2010 in the NutriNet-Santé Study, a general population-based e-cohort study. The Etude Nationale Nutrition Santé (ENNS; 2006-2007), a cross-sectional study with a nationally representative sample of 2,754 French adults aged 18-74 years, served as the reference data set. Reported dietary intakes from three 24-hour dietary records were weighted and compared between the two studies via Student t tests for mean location, using a >5% cutoff for establishing practically meaningful differences. We observed similar intakes as regards carbohydrates, total lipids, protein, and total energy. However, intakes of fruit and vegetables, fiber, vitamins B 6 , B 9 , C, D, and E, iron, and magnesium were higher in the e-cohort than in the ENNS, while intakes of alcohol and nonalcoholic beverages were lower in the e-cohort. Significant sex-specific differences were observed regarding vitamins A and B 12 , zinc, and potassium. True intake differences, mode effects, and volunteer bias might each contribute to explaining the findings. In the future, repeated use of the same tool in large e-cohorts with heterogeneous dietary exposures could serve research purposes and supplement group-level monitoring of dietary trends. The Author 2016. Published by Oxford University Press on behalf of the Johns Hopkins Bloomberg School of Public Health. All rights reserved. For permissions, please e-mail:

  9. Incretin secretion: direct mechanisms

    DEFF Research Database (Denmark)

    Balk-Møller, Emilie; Holst, Jens Juul; Kuhre, Rune Ehrenreich


    enzyme responsible for incretin degradation (dipeptidyl peptidase-4) is inhibited (drugs are already on the market) while the secretion of endogenous GLP-1 secretion is stimulated at the same time may prove particularly rewarding. In this section we review current knowledge on the mechanisms for direct......The incretin hormones glucose-dependent insulinotropic polypeptide (GIP) and glucagon-like peptide 1 (GLP-1) are secreted from gastro-intestinal K- and L-cells, respectively, and play an important role in post-prandial blood glucose regulation. They do this by direct stimulation of the pancreatic β....... This suggests that the therapeutic potential of GIP for the treatment for T2D is limited, whereas GLP-1 based treatments have been on the market since 2005. Research is now pursuing novel approaches to utilize the effects of GLP-1 for T2D treatment. A combinatorial approach by which the activity of the major...

  10. Direct thermal neutron capture

    International Nuclear Information System (INIS)

    Raman, S.; Kahane, S.; Lynn, J.E.


    We discuss the direct-capture theory pertaining to primary electric dipole (E1) transitions following slow-neutron capture. For light nuclides that we have studied (including 9 Be, 12 C, 13 C, 24 Mg, 25 Mg, 26 Mg, 32 S, 33 S, 34 S, 40 Ca, and 44 Ca), estimates of direct-capture cross sections using optical-model potentials with physically realistic parameters, are in reasonable agreement with the data. Minor disagreements that exist are consistent with extrapolations to light nuclides of generally accepted formulations of compound-nucleus capture. We also discuss the channel-capture approximation which is, in general, a good representation of these cross sections in heavier nuclei particularly if the scattering lengths are not different from the corresponding potential radii. We also draw attention to cases where the use of this formula leads to inaccurate predictions. 9 refs., 1 fig., 2 tab

  11. Incretin secretion: direct mechanisms

    DEFF Research Database (Denmark)

    Balk-Møller, Emilie; Holst, Jens Juul; Kuhre, Rune Ehrenreich


    The incretin hormones glucose-dependent insulinotropic polypeptide (GIP) and glucagon-like peptide 1 (GLP-1) are secreted from gastro-intestinal K- and L-cells, respectively, and play an important role in post-prandial blood glucose regulation. They do this by direct stimulation of the pancreatic β......-cell, accounting for some 25-70% of postprandial insulin secretion in healthy subjects. In patients with type 2 diabetes (T2D, however, this effect is greatly reduced or lost due to a combination of severely impaired or eliminated insulinotrophic effect of GIP and reduced meal stimulated GLP-1 secretion...... enzyme responsible for incretin degradation (dipeptidyl peptidase-4) is inhibited (drugs are already on the market) while the secretion of endogenous GLP-1 secretion is stimulated at the same time may prove particularly rewarding. In this section we review current knowledge on the mechanisms for direct...

  12. Direction sensitive neutron detector (United States)

    Ahlen, Steven; Fisher, Peter; Dujmic, Denis; Wellenstein, Hermann F.; Inglis, Andrew


    A neutron detector includes a pressure vessel, an electrically conductive field cage assembly within the pressure vessel and an imaging subsystem. A pressurized gas mixture of CF.sub.4, .sup.3He and .sup.4He at respective partial pressures is used. The field cage establishes a relatively large drift region of low field strength, in which ionization electrons generated by neutron-He interactions are directed toward a substantially smaller amplification region of substantially higher field strength in which the ionization electrons undergo avalanche multiplication resulting in scintillation of the CF.sub.4 along scintillation tracks. The imaging system generates two-dimensional images of the scintillation patterns and employs track-finding to identify tracks and deduce the rate and direction of incident neutrons. One or more photo-multiplier tubes record the time-profile of the scintillation tracks permitting the determination of the third coordinate.

  13. Direct use in Hawaii

    International Nuclear Information System (INIS)

    Beck, A.G.


    This paper reports on a public laboratory, Noi'i O Puna, that was established in Hawaii to support direct use research in 1985, tapping the previously unutilized heat in brines from the HGP-A well. Two rounds of small grants were offered to entrepreneurs. With the closure of the HGP-A power plant in late 1989, Noi'i O Puna is expanding its facilities. When the HGP-A well is back in service, Noi'i O Puna will be able to support additional research and development projects, as well as pre-commercial ventures. Direct use industries, which support existing agricultural activities in the region have good potential

  14. Future directions for QCD

    International Nuclear Information System (INIS)

    Bjorken, J.D.


    New directions for exploring QCD at future high-energy colliders are sketched. These include jets within jets. BFKL dynamics, soft and hard diffraction, searches for disoriented chiral condensate, and doing a better job on minimum bias physics. The new experimental opportunities include electron-ion collisions at HERA, a new collider detector at the C0 region of the TeVatron, and the FELIX initiative at the LHC

  15. Direct hydrocarbon fuel cells (United States)

    Barnett, Scott A.; Lai, Tammy; Liu, Jiang


    The direct electrochemical oxidation of hydrocarbons in solid oxide fuel cells, to generate greater power densities at lower temperatures without carbon deposition. The performance obtained is comparable to that of fuel cells used for hydrogen, and is achieved by using novel anode composites at low operating temperatures. Such solid oxide fuel cells, regardless of fuel source or operation, can be configured advantageously using the structural geometries of this invention.

  16. Estudio comparativo de la resolución de problemas en el rendimiento estudiantil en el contenido de electroquímica (COMPARATIVE STUDY OF THE RESOLUTION OF PROBLEMS IN THE STUDENT YIELD ON THE CONTENT OF ELECTROCHEMISTRY

    Directory of Open Access Journals (Sweden)

    Di’ Bacco Vera Lucia


    Full Text Available Resumen:Este estudio comparó las metodologías de resolución de problemas de: Reif, Durán y García, a través del rendimiento estudiantil en el contenido de electroquímica. La muestra estuvo representada por 73 estudiantes del Primer Año de Ciencias de la Unidad Educativa Nacional "El Eneal" del Municipio Crespo, Estado Lara-Venezuela, año escolar 2006-2007. Veinticinco (25 aprendices pertenecen al grupo experimental uno (GE1 y los grupos experimentales dos (GE2 y tres (GE3 están conformados por veinticuatro (24 estudiantes cada uno. Antes de la aplicación de las metodologías, se administró una prueba de conocimientos previos a los tres grupos experimentales; determinándose que los grupos son homogéneos. Al finalizar las tres metodologías, se les aplicó a los tres grupos una post-prueba. Los resultados permitieron concluir que no existe diferencia, estadísticamente significativa, entre el rendimiento estudiantil, en términos del promedio de calificaciones, por los tres grupos que recibieron los tratamientos con las tres estrategias de resolución de problemas utilizadas.Abstract:This study compared the methodologies of resolution of problems: Reif, and García Durán, through student performance on the content of electrochemistry. The sample was represented by 73 students from the First Year of Science Education National Unity "The Eneal" Crespo Municipio Crespo, Estado Lara-Venezuela, 2006-2007 school year. Twenty-five (25 trainees belong to an experimental group (GE1 and two experimental groups (GE2 and three (GE3 are composed of twenty-four (24 students each. Before the application of methodologies, were administered a test of knowledge prior to the three experimental groups, determined that the groups are homogeneous. At the end of the three methodologies were applied to all three groups a post-test.The results allowed concluding that statistically significant difference between the student yields in terms of the average of


    Directory of Open Access Journals (Sweden)



    par évaporation sur des substrats en verre présentent des coefficients d’absorption ( élevées de l’ordre de 5.104 cm-1. Le tracé de la fonction (h2 des couches minces recuites sous vide à différentes températures en fonction de l’énergie des photons incident a mis en relief la nature directe de la transition fondamentale est a permis également de calculer le gap Eg = 1.04 eV.

  18. Surface integral formulation of Maxwell's equations for simulation of non-destructive testing by eddy currents. Preliminary study on the implementation of the fast multipole method; Formulation integrale surfacique des equations de Maxwell pour la simulation de controles non destructifs par courant de Foucault. Etude preliminaire a la mise en oeuvre de la methode multipole rapide.

    Energy Technology Data Exchange (ETDEWEB)

    Lim, T.


    numeriquement un controle non destructif par courants de Foucault (CND-CF), la reponse du capteur peut etre modelisee via une approche semi-analytique par integrales de volume. Plus rapide que la methode des elements finis, cette approche est cependant limitee a l'etude de pieces planes ou cylindriques (sans prise en compte des effets de bords) du fait de la complexite de l'expression de la dyade de Green pour des configurations plus generales. Or, il existe une forte demande industrielle pour etendre les capacites de la modelisation CF a des configurations complexes (plaques deformees, bords de piece...). Nous avons donc ete amenes a formuler differemment le probleme electromagnetique, en nous fixant comme objectif de conserver une approche semi-analytique. La formulation integrale surfacique (SIE) permet d'exprimer le probleme volumique en un probleme de transmission equivalent a l'interface (2D) entre sous-domaines homogenes. Ce probleme est ramene a la resolution d'un systeme lineaire (par la methode des moments) dont le nombre d'inconnues est reduit du fait du caractere surfacique du maillage. Des lors, ce systeme peut etre resolu par un solveur direct pour de petites configurations. Cela nous a permis de traiter plusieurs seconds membres (ie. differentes positions de capteurs) pour une seule inversion de la matrice d'impedance. Les resultats numeriques obtenus au moyen de cette formulation concernent des plaques avec la prise en compte des effets de bords tels que l'arete et le coin. Ils sont en accord avec des resultats obtenus par la methode des elements finis. Pour des configurations de grandes tailles, nous avons mene une etude preliminaire a l'adaptation d'une methode d'acceleration du produit matrice-vecteur intervenant dans un solveur iteratif (methode multipole rapide, ou FMM) afin de definir les conditions dans lesquelles le calcul FMM fonctionne correctement (precision, convergence...) dans le contexte CND

  19. Contribution to the micro-calorimetric study of the characteristics of radio-elements and to their qualitative and quantitative analysis; Contribution a l'etude microcalorimetrique des caracteristiques des radio-elements et a leurs analyses qualitative et quantitative

    Energy Technology Data Exchange (ETDEWEB)

    Ozias, Y. [Centre de Production de Plutonium de Marcoule, 30 (France)


    accuracy equal to that obtained by mass spectrography (destruction of the sample) 1 to 3 per cent, and higher than that obtained by counting techniques (greater than 5 per cent). (author) [French] Le principe de cette etude consiste a enregistrer avec le microcalorimetre E. CALVET le flux d'energie emis par les radioelements en fonction du temps at a partir de cette courbe de determiner soit leurs caracteristiques (periode et energie du rayonnement), soit la composition d'un melange de radioelements. Dans une premiere partie on a adapte les relations theoriques de la radioactivite a l'etude microcalorimetrique. Dans une deuxieme partie on determine experimentalement au microcalorimetre E. CALVET les caracteristiques de divers radioelements, yttrium 90, phosphore 32, soufre 35, iode 131, etc. et leurs melanges. On a etudie plus particulierement l'analyse isotopique du melange de {sup 239}Pu, de {sup 240}Pu et eventuellement de {sup 241}Pu. La methode microcalorimetrique n'a pas la sensibilite des methodes classiques de comptage, sa limite actuelle para etre de l'ordre du micro-watt pour les appareils utilises, mais elle est la plus directe pour les emetteurs de rayonnements facilement absorbables({alpha} et {beta}). Pour les emetteurs {gamma} une partie seulement de l'energie est absorbee par les parois du recipient. La determination de leurs caracteristiques et de leurs masses dans les melanges ne depend ni de la forme, ni de la dilution, ni surtout de l'auto-absorption de la source. Pour des echantillons de forte activite, cette auto-absorption est pour les methodes classiques la source de grosses difficultes entra ant de multiples manipulations: divisions, mise en solution, dilutions qui introduisent autant de causes d'erreur. La methode calorimetrique permet de travailler sur l'echantillon brut. Toutes les mesures ont ete faites avec le microcalorimetre E. CALVET classique; mais pour effectuer une mesure tres precise de

  20. New rock salt-related oxides Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Laha, S. [Departamento de Químicas Inorganica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012 (India); Morán, E., E-mail: [Departamento de Químicas Inorganica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Sáez-Puche, R.; Alario-Franco, M.Á.; Dos santos-Garcia, A.J. [Departamento de Químicas Inorganica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain); Gonzalo, E.; Kuhn, A.; García-Alvarado, F. [Universidad CEU San Pablo, Facultad de Farmacia, Departamento de Química, 28668 Boadilla del Monte, Madrid (Spain); Sivakumar, T.; Tamilarasan, S.; Natarajan, S.; Gopalakrishnan, J. [Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012 (India)


    We describe the synthesis, crystal structure, magnetic and electrochemical characterization of new rock salt-related oxides of formula, Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni). The M=Co oxide adopts the LiCoO{sub 2} (R-3m) structure, where sheets of LiO{sub 6} and (Co{sub 2}/Ru)O{sub 6} octahedra are alternately stacked along the c-direction. The M=Ni oxide also adopts a similar layered structure related to Li{sub 2}TiO{sub 3}, where partial mixing of Li and Ni/Ru atoms lowers the symmetry to monoclinic (C2/c). Magnetic susceptibility measurements reveal that in Li{sub 3}Co{sub 2}RuO{sub 6}, the oxidation states of transition metal ions are Co{sup 3+} (S=0), Co{sup 2+} (S=1/2) and Ru{sup 4+} (S=1), all of them in low-spin configuration and at 10 K, the material orders antiferromagnetically. Analogous Li{sub 3}Ni{sub 2}RuO{sub 6} presents a ferrimagnetic behavior with a Curie temperature of 100 K. The differences in the magnetic behavior have been explained in terms of differences in the crystal structure. Electrochemical studies correlate well with both magnetic properties and crystal structure. Li-transition metal intermixing may be at the origin of the more impeded oxidation of Li{sub 3}Ni{sub 2}RuO{sub 6} when compared to Li{sub 3}Co{sub 2}RuO{sub 6}. Interestingly high first charge capacities (between ca. 160 and 180 mAh g{sup −1}) corresponding to ca. 2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory enough to consider these materials as alternatives to LiCoO{sub 2}. - Graphical abstract: Two new rock salt related oxides of formula, Li{sub 3}M{sub 2}RuO{sub 6}, (M=Co, Ni) have been prepared. The M=Co oxide adopts the LiCoO{sub 2} (R-3m) structure and the M=Ni oxide adopts a similar layered structure related to Li{sub 2}TiO{sub 3,} monoclinic (C2/c), with partial mixing of Li and Ni/Ru atoms. For Li{sub 3}Co{sub 2}RuO{sub 6}, oxidation state for Ru is 4+ and antiferromagnetic (AFM) order is