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Sample records for electrochemical surface derivation

  1. Electrochemical oxidation of hydrazine and its derivatives on the surface of metal electrodes in alkaline media

    NASA Astrophysics Data System (ADS)

    Asazawa, Koichiro; Yamada, Koji; Tanaka, Hirohisa; Taniguchi, Masatoshi; Oguro, Keisuke

    Electrochemical oxidation of hydrazine and its derivatives on the surface of various metal electrodes in alkaline media was investigated. A comparison of various polycrystalline metal electrodes (Ni, Co, Fe, Cu, Ag, Au, and Pt) showed that Co and Ni electrodes have a lower onset potential for hydrazine oxidation than the Pt electrode. The onset oxidation potential of APA (aminopolyacrylamide), a hydrazine derivative (-0.127 V vs. reversible hydrogen electrode, RHE), was similar to that of hydrazine hydrate (-0.178 V vs. RHE) in the case of the Co electrode. APA oxidation was possible because of hydrazine desorption that was caused by APA hydrolysis. The hydrolysis reaction was brought about by a heat treatment. This result suggests that the hydrazine hydrolysis reaction of hydrazine derivatives makes it possible to store hydrazine hydrate safely.

  2. Determining Electrochemical Surface Stress of Single Nanowires.

    PubMed

    Wang, Hui; Shan, Xiaonan; Yu, Hui; Wang, Yan; Schmickler, Wolfgang; Chen, Hong-Yuan; Tao, Nongjian

    2017-02-13

    Electrochemical surface stress is important in nanomaterials because of their large surface-to-volume ratios, which lead to unique mechanical and electrocatalytic properties, but directly measuring this quantity has been challenging. Here we report on experimental determination of the surface stress, and associated electrochemical processes of a single gold nanowire with an optical imaging technique. We show that surface stress changes linearly and reversibly with the potential between 0 and 0.8 V versus Ag/AgCl, but abruptly with large hysteresis, associated with the oxidation and reduction of the nanowire, between 0.8 and 1.5 V. The potential derivative of the surface stress closely resembles the cyclic voltammograms. We described the observations in terms of anion adsorption and surface oxidation/reduction. This work demonstrates a new approach to study electrochemical processes and the associated surface stress changes of nanomaterials.

  3. Electrochemical nitridation of metal surfaces

    DOEpatents

    Wang, Heli; Turner, John A.

    2015-06-30

    Electrochemical nitridation of metals and the produced metals are disclosed. An exemplary method of electrochemical nitridation of metals comprises providing an electrochemical solution at low temperature. The method also comprises providing a three-electrode potentiostat system. The method also comprises stabilizing the three-electrode potentiostat system at open circuit potential. The method also comprises applying a cathodic potential to a metal.

  4. In situ electrochemical surface derivation of cobalt phosphate from a Co(CO3)0.5(OH)·0.11H2O nanoarray for efficient water oxidation in neutral aqueous solution.

    PubMed

    Cui, Liang; Liu, Danni; Hao, Shuai; Qu, Fengli; Du, Gu; Liu, Jingquan; Asiri, Abdullah M; Sun, Xuping

    2017-03-02

    In this Communication, cobalt phosphate (Co-Pi) has been successfully developed on a Co(CO3)0.5(OH)·0.11H2O nanoarray (CCH NA) on Ti mesh in neutral phosphate-buffered solution (PBS) via in situ electrochemical surface derivation. The resulting core@shell structured CCH@Co-Pi NA/Ti exhibits remarkable activity toward water oxidation with the need of an overpotential of 460 mV to achieve a geometrical catalytic current density of 10 mA cm(-2) in 0.1 M PBS, with a high turnover frequency of and long-term electrochemical stability.

  5. Regioselective Green Electrochemical Approach to the Synthesis of Nitroacetaminophen Derivatives.

    PubMed

    Salahifar, Eslam; Nematollahi, Davood; Bayat, Mehdi; Mahyari, Amir; Amiri Rudbari, Hadi

    2015-10-02

    A regioselective green synthesis of nitroacetaminophen derivatives was carried out by electrochemical oxidation of acetaminophen, N-(2-hydroxyphenyl)acetamide, and 1-(4-(4-hydroxyphenyl)piperazin-1-yl)ethanone in the presence of nitrite ion as a nucleophile. The present work has led to the development of a reagentless green and facile electrochemical method for the synthesis of some nitroacetaminophen derivatives.

  6. Characterization of electrochemically modified polycrystalline platinum surfaces

    SciTech Connect

    Krebs, L.C.; Ishida, Takanobu

    1991-12-01

    The characterization of electrochemically modified polycrystalline platinum surfaces has been accomplished through the use of four major electrochemical techniques. These were chronoamperometry, chronopotentiommetry, cyclic voltammetry, and linear sweep voltammetry. A systematic study on the under-potential deposition of several transition metals has been performed. The most interesting of these were: Ag, Cu, Cd, and Pb. It was determined, by subjecting the platinum electrode surface to a single potential scan between {minus}0.24 and +1.25 V{sub SCE} while stirring the solution, that the electrocatalytic activity would be regenerated. As a consequence of this study, a much simpler method for producing ultra high purity water from acidic permanganate has been developed. This method results in water that surpasses the water produced by pyrocatalytic distillation. It has also been seen that the wettability of polycrystalline platinum surfaces is greatly dependent on the quantity of oxide present. Oxide-free platinum is hydrophobic and gives a contact angle in the range of 55 to 62 degrees. We have also modified polycrystalline platinum surface with the electrically conducting polymer poly-{rho}-phenylene. This polymer is very stable in dilute sulfuric acid solutions, even under applied oxidative potentials. It is also highly resistant to electrochemical hydrogenation. The wettability of the polymer modified platinum surface is severely dependent on the choice of supporting electrolyte chosen for the electrochemical polymerization. Tetraethylammonium tetrafluoroborate produces a film that is as hydrophobic as Teflon, whereas tetraethylammonium perchlorate produces a film that is more hydrophilic than oxide-free platinum.

  7. Electrochemical components employing polysiloxane-derived binders

    DOEpatents

    Delnick, Frank M.

    2013-06-11

    A processed polysiloxane resin binder for use in electrochemical components and the method for fabricating components with the binder. The binder comprises processed polysiloxane resin that is partially oxidized and retains some of its methyl groups following partial oxidation. The binder is suitable for use in electrodes of various types, separators in electrochemical devices, primary lithium batteries, electrolytic capacitors, electrochemical capacitors, fuel cells and sensors.

  8. Electric Arc and Electrochemical Surface Texturing Technologies

    NASA Technical Reports Server (NTRS)

    Banks, Bruce A.; Rutledge, Sharon K.; Snyder, Scott A.

    1997-01-01

    Surface texturing of conductive materials can readily be accomplished by means of a moving electric arc which produces a plasma from the environmental gases as well as from the vaporized substrate and arc electrode materials. As the arc is forced to move across the substrate surface, a condensate from the plasma re-deposits an extremely rough surface which is intimately mixed and attached to the substrate material. The arc textured surfaces produce greatly enhanced thermal emittance and hold potential for use as high temperature radiator surfaces in space, as well as in systems which use radiative heat dissipation such as computer assisted tomography (CAT) scan systems. Electrochemical texturing of titanium alloys can be accomplished by using sodium chloride solutions along with ultrasonic agitation to produce a random distribution of craters on the surface. The crater size and density can be controlled to produce surface craters appropriately sized for direct bone in-growth of orthopaedic implants. Electric arc texturing and electrochemical texturing techniques, surface properties and potential applications will be presented.

  9. Surface properties of electrochemically buffed titanium casting.

    PubMed

    Okawa, Seigo; Hossain, Awlad; Kanatani, Mitsugu; Watanabe, Kouichi; Miyakawa, Osamu

    2004-12-01

    Electrochemical buffing, a combined process of electrochemical and mechanical polishing, was applied to titanium casting. Mixture of alpha-Al2O3 suspension (average grain diameter of 5 microm) and 5% KNO3 solution was used as abrasive slurry. Specimen and experimental wheel buff were respectively connected to the positive and negative poles of a DC source, whose potential ratings ranged from 0 V (MEP) to 10 V (ECB10). Surface roughness, hardness, color, and cleanness were investigated. ECB10 surface produced a gold color and attained a mirror finish, as its roughness value was only one-quarter that of MEP. High amount of aluminum was present in MEP surface. Its bond state entirely differed from that of alpha-Al2O3, hence indicating surface alteration due to chemical reactions with the abrasive material. At higher potentials, reaction products might be dissolved anodically, so that the surface was chemically clean to some extent. The surface also became rich in OH-.

  10. Electrochemically enhanced surface plasticity of steels

    NASA Astrophysics Data System (ADS)

    Gutman, E. M.; Unigovski, Ya.; Shneck, R.; Ye, F.; Liang, Y.

    2016-12-01

    There are serious problems with the formability of alloys which are relatively hard and brittle below ambient temperatures, e.g., in cold extrusion and drawing processes. It is known that electrochemical surface treatment can decrease residual stresses and hardness of the surface layer as a result of the chemomechanical effect (CME), and also improve the plastic deformation ability, e.g., deep drawing of high-strength alloys. Plastic deformation ability of materials can be characterized by hardness measurements. The present study shows some possibilities to improve the surface ductility of carbon steels and FeSi6.5 steel under anodic polarization depending on the current density, composition and pH of acids and chloride electrolytes. The relative Vickers hardness (RVH) amounting to a squared ratio of the penetration depth of a cone indenter in air as compared to that in a solution (hair/hsol)2 was found as a function of the current density and the electrolyte composition. A decrease in hardness of the surface layer as a result of anodic electrochemical polarization was found for different steels.

  11. Electrochemical Potential Derived from Atomic Cluster Structures.

    PubMed

    Du, Jinglian; Xiao, Debao; Wen, Bin; Melnik, Roderick; Kawazoe, Yoshiyuki

    2016-02-04

    Based on the atomic cluster structures and free electron approximation model, it is revealed that the electrochemical potential (ECP) for the system of interest is proportional to the reciprocal of atomic cluster radius squared, i.e., φ = k·(1/r(2)). Applied to elemental crystals, the correlation between atomic cluster radii and the ECP that we have predicted agrees well with the previously reported results. In addition, some other physicochemical properties associated with the ECP have also been found relevant to the atomic cluster radii of materials. Thus, the atomic cluster radii can be perceived as an effective characteristic parameter to measure the ECP and related properties of materials. Our results provide a better understanding of ECP directly from the atomic structures perspective.

  12. Electrochemically polymerized conjugated polymer films: Stability improvement and surface functionalization

    NASA Astrophysics Data System (ADS)

    Wei, Bin

    Conjugated polymers have been widely used in various applications including organic solar cells, electrochromic devices, chemical sensors, and biomedical devices. Poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives have received considerable interest because of their low oxidation potential, relatively high chemical stability, and high conductivity. Electrochemical deposition is a convenient method for precisely fabricating conjugated polymer thin films. Here, we report the stability improvement and surface functionalization of electrochemically polymerized PEDOT films. The long-term performance of PEDOT coatings is limited by their relatively poor stability on various inorganic substrates. Two different methods were used to improve the stability of PEDOT coatings, one involved using carboxylic acid functionalized EDOT (EDOT-acid) as adhesion promoter. EDOT-acid molecules were chemically bonded onto activated metal oxide substrates via chemisorption. PEDOT was then polymerized onto the EDOT-acid modified substrates, forming covalently bonded coatings. An aggressive ultrasonication test confirmed the significantly improved adhesion of the PEDOT films on electrodes with EDOT-acid treatment over those without treatment. The other method was to use an octa-ProDOT-functionalized POSS derivative (POSSProDOT) as cross-linker. PEDOT copolymer films were electrochemically deposited with various concentrations of POSS-ProDOT. The optical, morphological and electrochemical properties of the copolymer films could be systematically tuned with the incorporation of POSS-ProDOT. Significantly enhanced electrochemical and mechanical stability of the copolymers were observed at intermediate levels of POSS-ProDOT content (3.1 wt%) via chronic stimulation tests. Surface functionalization of conducting polymer films provides a potential means for systematically tailoring their chemical and physical properties. We have synthesized, polymerized and characterized a dialkene

  13. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Li, Jun; Zhu, Ximeng; Bodily, D.M.; Liang, Jun; Zhong, Tingke; Wadsworth, M.E.

    1991-01-01

    The ongoing work includes the characterization of coal pyrites, the floatability evaluation of three typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces. This report contains three sections, Transpassive Oxidation of Pyrite,'' Flotation and Electrochemical Pretreatment,'' and Flotation Kinetics of Coal and Coal Pyrite.''

  14. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Zhu, Ximeng; Bodily, D.M.; Wadsworth, M.E.

    1990-01-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  15. Computational and experimental evaluation of selective substitution of thiolated coumarin derivatives on gold nanoparticles: Surface enhancing Raman scattering and electrochemical studies

    NASA Astrophysics Data System (ADS)

    Mlambo, Mbuso; Harris, Richard A.; Mashazi, Philani; Sabela, Myalowenkosi; Kanchi, Suvardhan; Madikizela, Lawrence M.; Shumbula, Prince N.; Moloto, Nosipho; Hlatshwayo, Thulani T.; Mdluli, Phumlani S.

    2017-02-01

    Gold nanoparticles (AuNPs) of various sizes were prepared and treated with a mixture of HS-(CH2)11-NHCO-coumarin (act as Raman reporter) and HS-PEG-(CH2)11COOH (as co-stabilizer and also to attach biomarkers on activated sbnd COOH) to produce mixed monolayer protected clusters of gold (AuMMPCs). In this paper, we demonstrate the significance of the HS-(CH2)11-NHCO-coumarin concentration (percentage ratio) on the enhancement factor (EF), and the geometry of the adsorbed ligands on AuNPs of different sizes. The calculated EFs from Raman spectra reveal a significant decrease with an increase in AuNPs sizes. Molecular dynamics calculations were carried out to obtain the adsorption energies for different ratios of HS-PEG-(CH2)11COOH to HS-(CH2)11-NHCO-coumarin. It was found that molecules that adsorb strongly on the surface of the metal, underwent changes in their polarizability and consequently enhanced Raman intensities were observed, and this was in agreement with experimental data.

  16. GaN surface states investigated by electrochemical studies

    NASA Astrophysics Data System (ADS)

    Winnerl, Andrea; Garrido, Jose A.; Stutzmann, Martin

    2017-03-01

    We present a systematic study of electrochemically active surface states on MOCVD-grown n-type GaN in aqueous electrolytes using cyclic voltammetry and impedance spectroscopy over a wide range of potentials and frequencies. In order to alter the surface states, the GaN samples are either etched or oxidized, and the influence of the surface treatment on the defect-mediated charge transfer to the electrolyte is investigated. Etching in HCl removes substoichiometric GaO x , and leads to a pronounced density of electrochemically active surface states. Oxidation effectively removes these surface states.

  17. Electrochemical synthesis and surface characterization of (pyrrole+2-methylfuran) copolymer

    NASA Astrophysics Data System (ADS)

    Djaouane, Linda; Nessark, Belkacem; Sibous, Lakhdar

    2017-02-01

    Electrochemical copolymerization of pyrrole (Py) and 2-methylfuran (2 MF) was performed on platinum and ITO substrates in acetonitrile/lithium perchlorate solution, using cyclic voltammetry method. The electrochemical behavior of the modified electrode surface by polypyrrole, poly(2-methylfuran) homopolymers and (pyrrole+2-methylfuran) copolymer was characterized by cyclic voltammetry, electrochemical impedance spectroscopy (EIS), UV-visible spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM). The cyclic voltammetry shows anodic and cathodic peaks which are characteristic of the oxidation and the reduction of the formed films. The electrochemical impedance spectroscopy confirmed the results obtained by cyclic voltammetry. AFM and SEM analyses proved as well that the morphology and the electrochemical properties of the polypyrrole film are modified in the presence of 2-methylfuran.

  18. Electrochemical behavior of carbon aerogels derived from different precursors

    SciTech Connect

    Pekala, R.W.; Alviso, C.T.; Nielsen, J.K.; Tran, T.D.; Reynolds, G.A.M.; Dresselhaus, M.S.

    1995-12-31

    The ability to tailor the structure and properties of porous carbons has led to their increased use as electrodes in energy storage devices. The research focuses on the synthesis and characterization of carbon aerogels for use in electrochemical double layer capacitors.Carbon aerogels are formed from the sol-gel polymerization of (1) resorcinol-formaldehyde or (2) phenolic-furfural, followed by supercritical drying from carbon dioxide, and subsequent pyrolysis in an inert atmosphere. These materials can be produced as monoliths, composites, thin films, powders, or microspheres. In all cases, the aerogels have an open-cell structure with an ultrafine pore size (< 100 nm), high surface area (400--1,100 m{sup 2}/g), and a solid matrix composed of interconnected particles, fibers, or platelets with characteristic dimensions of 10 nm. This paper examines the effects of the carbon precursor and processing conditions on electrochemical performance in aqueous and organic electrolytes.

  19. Electrochemical behavior of carbon aerogels derived from different precursors

    SciTech Connect

    Pekala, R.W.; Alviso, C.T.; Nielson, J.K.; Tran, T.D.; Reynolds, G.M.; Dresshaus, M.S.

    1995-04-01

    The ability to tailor the structure and properties of porous carbons has led to their increased use as electrodes in energy storage devices. Our research focuses on the synthesis and characterization of carbon aerogels for use in electrochemical double layer capacitors. Carbon aerogels are formed from the sol-gel polymerization of (1) resorcinol-formaldehyde or (2) phenolic-furfural, followed by supercritical drying from carbon dioxide, and subsequent pyrolysis in an inert atmosphere. These materials can be produced as monoliths, composites, thin films, powders, or microspheres. In all cases, the areogels have an open-cell structure with an ultrafine pore size (<100 nm), high surface area (400-1 100 m{sup 2}/g), and a solid matrix composed of interconnected particles, fibers, or platelets with characteristic dimensions of 10 nm. This paper examines the effects of the carbon precursor and processing conditions on electrochemical performance in aqueous and organic electrolytes.

  20. Chemical imaging of surfaces with the scanning electrochemical microscope

    NASA Astrophysics Data System (ADS)

    Bard, Allen J.; Fan, Fu-Ren F.; Pierce, David T.; Unwin, Patrick R.; Wipf, David O.; Zhou, Feimeng

    1991-10-01

    Scanning electrochemical microscopy is a scanning probe technique that is based on faradaic current changes as a small electrode is moved across the surface of a sample. The images obtained depend on the sample topography and surface reactivity. The response of the scanning electrochemical microscope is sensitive to the presence of conducting and electroactive species, which makes it useful for imaging hetrogeneous surfaces. The principles and instrumentation used to obtain images and surface reaction-kinetic information are discussed, and examples of applications to the study of electrodes, minerals, and biological samples are given.

  1. In-Situ Electrochemical Surface Science

    DTIC Science & Technology

    1993-04-01

    upd ( underpotential deposited ) metals. The examples are chosen in part to illustrate the value of combined electrochemical and STM data, and the...submonolayer deposits at electrode potentials that can be substantially less negative than required for multilayer ("bulk-phase") metal deposition [59...also affects greatly the copper upd structure[57], which in turn can influence the morphology of subsequent multilayer copper depositions [57b]. The

  2. Oxide modified air electrode surface for high temperature electrochemical cells

    DOEpatents

    Singh, Prabhakar; Ruka, Roswell J.

    1992-01-01

    An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

  3. Surface electrochemical control for the fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Zhu, Ximeng; Li, Jun; Bodily, D.M.; Liang, Jun; Zhong, Tingke; Wadsworth, M.E.

    1992-01-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  4. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Bodily, D.M.; Wadsworth, M.E.

    1990-01-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  5. Surface electrochemical control for the fine coal and pyrite separation

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Wadsworth, M.E.

    1989-01-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  6. Electrochemical planarization of copper surfaces with submicron features

    SciTech Connect

    Chalupa, R.; Andryushchenko, T.; Han, J.; Ghosh, T.; Shankar, S.; Fischer, P.

    2007-07-15

    Electrochemical planarization (ECP) of copper surfaces in a phosphoric acid-based electrolyte solution is discussed. A first-principles, quantum chemistry modeling work is presented that further validates the water-facilitated (and water rate limited) chemistry model for copper oxidation at the anode. This model has been previously deduced by other researchers [R. Vidal and A. West, J. Electrochem. Soc. 142, 2689 (1995); B. Du and I. I. Suni, J. Appl. Electrochem. 34, 1215 (2004); R. Vidal and A. West J. Electrochem. Soc. 142, 2682 (1995)] based on electrochemical experiments. Resulting water-limited model is validated against experimental data and applied to study the planarization behavior of a set of surface features. Aspect ratios and dimensions of these features were chosen to represent realistic (nonidealized, low aspect ratio structures) post-Damascene electroplate surface topography. Results are presented in a form of remaining feature amplitude versus mean copper thickness removed [A. C. West et al., J. Electrochem. Soc. 152, C652 (2005)]--allowing at-a-glance evaluation of the process against desired targets. The dominant effects of the mass transport boundary layer (BL) thickness on this planarization efficiency are discussed as are the challenges seen at typical flow conditions in ECP systems. Impact of changing the BL thickness and the requisite modulation of flow conditions analysis is included. Insights into practical challenges associated with BL buildup transient and associated surface roughening are summarized [D. Padhi et al., J. Electrochem. Soc. 150, 610 (2003)]. Challenges of applying ECP as a straightforward substitute to the robust chemical mechanical polish (CMP) process are significant. Practical modifications to upstream process flow to enable ECP would include optimized electroplating process or a CMP preprocessing step.

  7. In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

    PubMed

    Chen, Daqun; Hu, Weihua

    2017-03-28

    Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of homogeneous polymerization and heterogeneous system (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by self-assembled monolayer of ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information on eSI-ATRP, and offers a powerful platform for in situ investigation of such complicated processes.

  8. Surface Modification of Nitinol by Chemical and Electrochemical Etching

    NASA Astrophysics Data System (ADS)

    Yang, Zhendi; Wei, Xiaojin; Cao, Peng; Gao, Wei

    2013-07-01

    In this paper, Nitinol, an equiatomic binary alloy of nickel and titanium, was surface modified for its potential biomedical applications by chemical and electrochemical etching. The main objective of the surface modification is to reduce the nickel content on the surface of Nitinol and simultaneously to a rough surface microstructure. As a result, better biocompatibility and better cell attachment would be achieved. The effect of the etching parameters was investigated, using scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometry (EDX) and X-ray photoelectron spectrometry (XPS). The corrosion property of modified Nitinol surfaces was investigated by electrochemical work station. After etching, the Ni content in the surface layer has been reduced and the oxidation of Ti has been enhanced.

  9. Hydrophilic graphene surface prepared by electrochemically reduced micellar graphene oxide as a platform for electrochemical sensor.

    PubMed

    Akkarachanchainon, Nontapol; Rattanawaleedirojn, Pranee; Chailapakul, Orawon; Rodthongkum, Nadnudda

    2017-04-01

    Graphene is one of the promising hydrophobic carbon-based nanomaterials used for electrode modification in electrochemical sensor. However, hydrophobicity of graphene makes it incompatible with aqueous electrolyte solution, leading to significant impediment to the electron transfer process. Here, we aim to alter graphene property to be hydrophilicity by using an electrochemically reduced micellar graphene oxide for electrode surface modification. Then, this system was applied for the simultaneous determination of toxic pesticides (e.g. carbofuran and carbendazim). Interestingly, the modified electrode offers an improved electrochemical sensitivity, verified by a drastic increase in current signal of carbofuran (4 times) and carbendazim (12 times) compared to an unmodified electrode. Under the optimal conditions, low detection limits of carbofuran and carbendazim were found to be 10µgL(-1) and 5µgL(-1), respectively. Ultimately, this system was successfully applied for the sensitive and simultaneous determination of carbofuran and carbendazim residues in various agricultural products.

  10. Reactivity mapping with electrochemical gradients for monitoring reactivity at surfaces in space and time.

    PubMed

    Krabbenborg, Sven O; Nicosia, Carlo; Chen, Pengkun; Huskens, Jurriaan

    2013-01-01

    Studying and controlling reactions at surfaces is of great fundamental and applied interest in, among others, biology, electronics and catalysis. Because reaction kinetics is different at surfaces compared with solution, frequently, solution-characterization techniques cannot be used. Here we report solution gradients, prepared by electrochemical means, for controlling and monitoring reactivity at surfaces in space and time. As a proof of principle, electrochemically derived gradients of a reaction parameter (pH) and of a catalyst (Cu(I)) have been employed to make surface gradients on the micron scale and to study the kinetics of the (surface-confined) imine hydrolysis and the copper(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition, respectively. For both systems, the kinetic data were spatially visualized in a two-dimensional reactivity map. In the case of the copper(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition, the reaction order (2) was deduced from it.

  11. Effects of adding ethanol to KOH electrolyte on electrochemical performance of titanium carbide-derived carbon

    NASA Astrophysics Data System (ADS)

    Xu, Jiang; Zhang, Ruijun; Chen, Peng; Ge, Shanhai

    2014-01-01

    Porous carbide-derived carbons (CDCs) are synthesized from TiC at different chlorination temperatures as electrode materials for electrochemical capacitors. It is found that the microstructure of the produced CDCs has significant influence on both the hydrophilicity in aqueous KOH electrolyte and the resultant electrochemical performance. Because the TiC-CDC synthesized at higher temperature (e.g. 1000 °C) contains well-ordered graphite ribbons, it shows lower hydrophilicity and specific capacitance. It is also found that addition of a small amount of ethanol to KOH electrolyte effectively improves the wettability of the CDCs synthesized at higher temperature and the corresponding specific capacitance. Compared with the CDC synthesized at 600 °C, the CDC synthesized at 1000 °C shows fast ion transport and excellent capacitive behavior in KOH electrolyte with addition of ethanol because of the existences of mesopores and high specific surface area.

  12. Nanotubular surface modification of metallic implants via electrochemical anodization technique.

    PubMed

    Wang, Lu-Ning; Jin, Ming; Zheng, Yudong; Guan, Yueping; Lu, Xin; Luo, Jing-Li

    2014-01-01

    Due to increased awareness and interest in the biomedical implant field as a result of an aging population, research in the field of implantable devices has grown rapidly in the last few decades. Among the biomedical implants, metallic implant materials have been widely used to replace disordered bony tissues in orthopedic and orthodontic surgeries. The clinical success of implants is closely related to their early osseointegration (ie, the direct structural and functional connection between living bone and the surface of a load-bearing artificial implant), which relies heavily on the surface condition of the implant. Electrochemical techniques for modifying biomedical implants are relatively simple, cost-effective, and appropriate for implants with complex shapes. Recently, metal oxide nanotubular arrays via electrochemical anodization have become an attractive technique to build up on metallic implants to enhance the biocompatibility and bioactivity. This article will thoroughly review the relevance of electrochemical anodization techniques for the modification of metallic implant surfaces in nanoscale, and cover the electrochemical anodization techniques used in the development of the types of nanotubular/nanoporous modification achievable via electrochemical approaches, which hold tremendous potential for bio-implant applications. In vitro and in vivo studies using metallic oxide nanotubes are also presented, revealing the potential of nanotubes in biomedical applications. Finally, an outlook of future growth of research in metallic oxide nanotubular arrays is provided. This article will therefore provide researchers with an in-depth understanding of electrochemical anodization modification and provide guidance regarding the design and tuning of new materials to achieve a desired performance and reliable biocompatibility.

  13. Nanotubular surface modification of metallic implants via electrochemical anodization technique

    PubMed Central

    Wang, Lu-Ning; Jin, Ming; Zheng, Yudong; Guan, Yueping; Lu, Xin; Luo, Jing-Li

    2014-01-01

    Due to increased awareness and interest in the biomedical implant field as a result of an aging population, research in the field of implantable devices has grown rapidly in the last few decades. Among the biomedical implants, metallic implant materials have been widely used to replace disordered bony tissues in orthopedic and orthodontic surgeries. The clinical success of implants is closely related to their early osseointegration (ie, the direct structural and functional connection between living bone and the surface of a load-bearing artificial implant), which relies heavily on the surface condition of the implant. Electrochemical techniques for modifying biomedical implants are relatively simple, cost-effective, and appropriate for implants with complex shapes. Recently, metal oxide nanotubular arrays via electrochemical anodization have become an attractive technique to build up on metallic implants to enhance the biocompatibility and bioactivity. This article will thoroughly review the relevance of electrochemical anodization techniques for the modification of metallic implant surfaces in nanoscale, and cover the electrochemical anodization techniques used in the development of the types of nanotubular/nanoporous modification achievable via electrochemical approaches, which hold tremendous potential for bio-implant applications. In vitro and in vivo studies using metallic oxide nanotubes are also presented, revealing the potential of nanotubes in biomedical applications. Finally, an outlook of future growth of research in metallic oxide nanotubular arrays is provided. This article will therefore provide researchers with an in-depth understanding of electrochemical anodization modification and provide guidance regarding the design and tuning of new materials to achieve a desired performance and reliable biocompatibility. PMID:25258532

  14. Surface Chemistry in Electrochemical Atomic Layer Processing

    DTIC Science & Technology

    2007-11-02

    example, where a thin film of a material is formed an atomic layer at a time. That is, surface limited reactions are used to deposit individual atomic...The present studies were designed to investigate these surface limited reactions. To determine what the structures of the deposits were, and how that structure influenced subsequent deposition .

  15. Electrochemical capacitors utilizing low surface area carbon fiber

    SciTech Connect

    Lipka, S.M.

    1997-12-01

    The performance of electrochemical capacitors containing different commercial carbon fibers is reviewed. High specific capacitances (ca. 300 F/g) are obtained with low surface area carbon fiber (<1 m2/g) using a proprietary activation process. Capacitance is primarily achieved through pseudocapacitance resulting from surface functional groups. The performance of these devices is dependent on the type of carbon fiber, its carbon content, aspect ratio and microstructure. These devices can achieve high cycle life (ca. 100k) without significant loss in capacitance.

  16. Surface electrochemical control for fine coal and pyrite separation

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Riley, A.; Zhu, Ximeng; Bodily, D.M.; Liang, Jun; Zhong, Tinghe; Wadsworth, M.E.

    1991-01-01

    This technical progress report, prepared in accordance with the reporting requirements of DOE Project No. DE-AC22-89PC89758, covers the work performed from April 1, 1991 to June 30, 1991. The ongoing work includes the characterization of coal pyrites, the floatability evaluation of three typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces. 6 refs., 20 figs.

  17. Electrochemical characterization of gelatinized starch dispersions: voltammetry and electrochemical impedance spectroscopy on platinum surface.

    PubMed

    Hernandez-Jaimes, C; Lobato-Calleros, C; Sosa, E; Bello-Pérez, L A; Vernon-Carter, E J; Alvarez-Ramirez, J

    2015-06-25

    The electrochemical properties of gelatinized starch dispersions (GSD; 5% w/w) from different botanical sources were studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests over a platinum surface. The phenomenological modelling of EIS data using equivalent circuits indicated that after gelatinization the electrical resistance was determined mainly by the resistance of insoluble material (i.e., ghosts). Sonication of the GSD disrupted the ghost microstructure, and produced an increase in electrical conductivity by reducing the resistance of the insoluble material. The CV data showed three oxidation peaks at potentials where glucose solutions displayed oxidation waves. It is postulated that hydrolysis at the bulk and electrocatalyzed oxidation on the Pt-surface are reactions involved in the starch transformation. Starches peak intensity increased with the amylose content, suggesting that the amylose-rich matrix played an important role in the charge transfer in the electrolytic system.

  18. Characterization of Copper Corrosion Products in Drinking Water by Combining Electrochemical and Surface Analyses

    EPA Science Inventory

    This study focuses on the application of electrochemical approaches to drinking water copper corrosion problems. Applying electrochemical approaches combined with copper solubility measurements, and solid surface analysis approaches were discussed. Tafel extrapolation and Electro...

  19. Characterization of Copper Corrosion Products Formed in Drinking Water by Combining Electrochemical and Surface Analyses

    EPA Science Inventory

    This study focuses on the application of electrochemical approaches to drinking water copper corrosion problems. Applying electrochemical approaches combined with copper solubility measurements, and solid surface analysis approaches were discussed. Tafel extrapolation and Electro...

  20. Surface functionalisation of carbon for low cost fabrication of highly stable electrochemical DNA sensors.

    PubMed

    Debela, Ahmed M; Ortiz, Mayreli; Beni, Valerio; O'Sullivan, Ciara K

    2015-09-15

    An alternative strategy for surface tethering of DNA probes, where highly reactive glassy carbon (GC) substrates are prepared via electrochemical hydrogenation and electrochemical/chemical chlorination is reported. Thiolated DNA probes and alkanethiols were stably immobilised on the halogenated carbon, with electrochemical chlorination being milder, thus producing less damage to the surface. Electrochemical DNA sensors prepared using this surface chemistry on carbon with electrochemical chlorination providing an improved performance, producing a highly ordered surface and the use of lateral spacers to improve steric accessibility to immobilised probes was not required.

  1. New insights into the electrochemical behavior of acid orange 7: Convergent paired electrochemical synthesis of new aminonaphthol derivatives

    PubMed Central

    Momeni, Shima; Nematollahi, Davood

    2017-01-01

    Electrochemical behavior of acid orange 7 has been exhaustively studied in aqueous solutions with different pH values, using cyclic voltammetry and constant current coulometry. This study has provided new insights into the mechanistic details, pH dependence and intermediate structure of both electrochemical oxidation and reduction of acid orange 7. Surprisingly, the results indicate that a same redox couple (1-iminonaphthalen-2(1H)-one/1-aminonaphthalen-2-ol) is formed from both oxidation and reduction of acid orange 7. Also, an additional purpose of this work is electrochemical synthesis of three new derivatives of 1-amino-4-(phenylsulfonyl)naphthalen-2-ol (3a–3c) under constant current electrolysis via electrochemical oxidation (and reduction) of acid orange 7 in the presence of arylsulfinic acids as nucleophiles. The results indicate that the electrogenerated 1-iminonaphthalen-2(1 H)-one participates in Michael addition reaction with arylsulfinic acids to form the 1-amino-3-(phenylsulfonyl)naphthalen-2-ol derivatives. The synthesis was carried out in an undivided cell equipped with carbon rods as an anode and cathode. PMID:28165049

  2. New insights into the electrochemical behavior of acid orange 7: Convergent paired electrochemical synthesis of new aminonaphthol derivatives.

    PubMed

    Momeni, Shima; Nematollahi, Davood

    2017-02-06

    Electrochemical behavior of acid orange 7 has been exhaustively studied in aqueous solutions with different pH values, using cyclic voltammetry and constant current coulometry. This study has provided new insights into the mechanistic details, pH dependence and intermediate structure of both electrochemical oxidation and reduction of acid orange 7. Surprisingly, the results indicate that a same redox couple (1-iminonaphthalen-2(1H)-one/1-aminonaphthalen-2-ol) is formed from both oxidation and reduction of acid orange 7. Also, an additional purpose of this work is electrochemical synthesis of three new derivatives of 1-amino-4-(phenylsulfonyl)naphthalen-2-ol (3a-3c) under constant current electrolysis via electrochemical oxidation (and reduction) of acid orange 7 in the presence of arylsulfinic acids as nucleophiles. The results indicate that the electrogenerated 1-iminonaphthalen-2(1 H)-one participates in Michael addition reaction with arylsulfinic acids to form the 1-amino-3-(phenylsulfonyl)naphthalen-2-ol derivatives. The synthesis was carried out in an undivided cell equipped with carbon rods as an anode and cathode.

  3. New insights into the electrochemical behavior of acid orange 7: Convergent paired electrochemical synthesis of new aminonaphthol derivatives

    NASA Astrophysics Data System (ADS)

    Momeni, Shima; Nematollahi, Davood

    2017-02-01

    Electrochemical behavior of acid orange 7 has been exhaustively studied in aqueous solutions with different pH values, using cyclic voltammetry and constant current coulometry. This study has provided new insights into the mechanistic details, pH dependence and intermediate structure of both electrochemical oxidation and reduction of acid orange 7. Surprisingly, the results indicate that a same redox couple (1-iminonaphthalen-2(1H)-one/1-aminonaphthalen-2-ol) is formed from both oxidation and reduction of acid orange 7. Also, an additional purpose of this work is electrochemical synthesis of three new derivatives of 1-amino-4-(phenylsulfonyl)naphthalen-2-ol (3a–3c) under constant current electrolysis via electrochemical oxidation (and reduction) of acid orange 7 in the presence of arylsulfinic acids as nucleophiles. The results indicate that the electrogenerated 1-iminonaphthalen-2(1 H)-one participates in Michael addition reaction with arylsulfinic acids to form the 1-amino-3-(phenylsulfonyl)naphthalen-2-ol derivatives. The synthesis was carried out in an undivided cell equipped with carbon rods as an anode and cathode.

  4. The thermodynamics of proton hydration and the electrochemical surface potential of water

    SciTech Connect

    Pollard, Travis P.; Beck, Thomas L.

    2014-11-14

    The free energy change for transferring a single ion across the water liquid/vapor interface includes an electrochemical surface potential contribution. Since this potential is not directly accessible to thermodynamic measurement, several extra-thermodynamic approaches have been employed to infer its sign and magnitude, with a resulting wide spread of values. Here, we examine further the thermodynamics of proton hydration and the electrochemical surface potential of water along three directions: (1) a basic relation of interfacial electrostatics and experimental results on ion distributions near a water/organic interface are employed to infer a solvent contribution to the electrochemical surface potential, (2) a re-analysis is performed of the existing bulk and cluster ion hydration data, and (3) extensive computational modeling is conducted to examine the size dependence of hydration enthalpy differences for the NaF ion pair between the small cluster and the converged bulk limits. The computational studies include classical polarizable models and high-level quantum chemical methods. The new theoretical analysis of existing experimental data and the combined classical/quantum modeling lead to results consistent with our previously derived proton hydration quantities.

  5. Electrochemical characterization of organosilane-functionalized nanostructured ITO surfaces

    NASA Astrophysics Data System (ADS)

    Pruna, R.; Palacio, F.; López, M.; Pérez, J.; Mir, M.; Blázquez, O.; Hernández, S.; Garrido, B.

    2016-08-01

    The electroactivity of nanostructured indium tin oxide (ITO) has been investigated for its further use in applications such as sensing biological compounds by the analysis of redox active molecules. ITO films were fabricated by using electron beam evaporation at different substrate temperatures and subsequently annealed for promoting their crystallization. The morphology of the deposited material was monitored by scanning electron microscopy, confirming the deposition of either thin films or nanowires, depending on the substrate temperature. Electrochemical surface characterization revealed a 45 % increase in the electroactive surface area of nanostructured ITO with respect to thin films, one third lower than the geometrical surface area variation determined by atomic force microscopy. ITO surfaces were functionalized with a model organic molecule known as 6-(ferrocenyl)hexanethiol. The chemical attachment was done by means of a glycidoxy compound containing a reactive epoxy group, the so-called 3-glycidoxypropyltrimethoxy-silane. ITO functionalization was useful for determining the benefits of nanostructuration on the surface coverage of active molecules. Compared to ITO thin films, an increase in the total peak height of 140 % was observed for as-deposited nanostructured electrodes, whereas the same measurement for annealed electrodes resulted in an increase of more than 400 %. These preliminary results demonstrate the ability of nanostructured ITO to increase the surface-to-volume ratio, conductivity and surface area functionalization, features that highly benefit the performance of biosensors.

  6. Polypeptide Functional Surface for the Aptamer Immobilization: Electrochemical Cocaine Biosensing.

    PubMed

    Bozokalfa, Guliz; Akbulut, Huseyin; Demir, Bilal; Guler, Emine; Gumus, Z Pınar; Odaci Demirkol, Dilek; Aldemir, Ebru; Yamada, Shuhei; Endo, Takeshi; Coskunol, Hakan; Timur, Suna; Yagci, Yusuf

    2016-04-05

    Electroanalytical technologies as a beneficial subject of modern analytical chemistry can play an important role for abused drug analysis which is crucial for both legal and social respects. This article reports a novel aptamer-based biosensing procedure for cocaine analysis by combining the advantages of aptamers as selective recognition elements with the well-known advantages of biosensor systems such as the possibility of miniaturization and automation, easy fabrication and modification, low cost, and sensitivity. In order to construct the aptasensor platform, first, polythiophene bearing polyalanine homopeptide side chains (PT-Pala) was electrochemically coated onto the surface of an electrode and then cocaine aptamer was attached to the polymer via covalent conjugation chemistry. The stepwise modification of the surface was confirmed by electrochemical characterization. The designed biosensing system was applied for the detection of cocaine and its metabolite, benzoylecgonine (BE), which exhibited a linear correlation in the range from 2.5 up to 10 nM and 0.5 up to 50 μM for cocaine and BE, respectively. In order to expand its practical application, the proposed method was successfully tested for the analysis of synthetic biological fluids.

  7. A multimodal optical and electrochemical device for monitoring surface reactions: redox active surfaces in porous silicon Rugate filters.

    PubMed

    Ciampi, Simone; Guan, Bin; Darwish, Nadim A; Zhu, Ying; Reece, Peter J; Gooding, J Justin

    2012-12-21

    Herein, mesoporous silicon (PSi) is configured as a single sensing device that has dual readouts; as a photonic crystal sensor in a Rugate filter configuration, and as a high surface area porous electrode. The as-prepared PSi is chemically modified to provide it with stability in aqueous media and to allow for the subsequent coupling of chemical species, such as via Cu(I)-catalyzed cycloaddition reactions between 1-alkynes and azides ("click" reactions). The utility of the bimodal capabilities of the PSi sensor for monitoring surface coupling procedures is demonstrated by the covalent coupling of a ferrocene derivative, as well as by demonstrating ligand-exchange reactions (LER) at the PSi surface. Both types of reactions were monitored through optical reflectivity measurements, as well as electrochemically via the oxidation/reduction of the surface tethered redox species.

  8. BOREAS Derived Surface Meteorological Data

    NASA Technical Reports Server (NTRS)

    Hall, Forrest G. (Editor); Newcomer, Jeffrey A. (Editor); Twine, Tracy; Rinker, Donald; Knapp, David

    2000-01-01

    In 1995, the BOREAS science teams identified the need for a continuous surface meteorological and radiation data set to support flux and surface process modeling efforts. This data set contains actual, substituted, and interpolated 15-minute meteorological and radiation data compiled from several surface measurements sites over the BOREAS SSA and NSA. Temporally, the data cover 01-Jan-1994 to 31-Dec-1996. The data are stored in tabular ASCII files, and are classified as AFM-Staff data.

  9. Performance of carbon material derived from starch mixed with flame retardant as electrochemical capacitor

    NASA Astrophysics Data System (ADS)

    Tsubota, Toshiki; Morita, Masaki; Murakami, Naoya; Ohno, Teruhisa

    2014-12-01

    Carbon materials derived from starch with an added flame retardant, such as melamine polyphosphate, melamine sulfate, guanylurea phosphate, or guanidine phosphate, were synthesized for investigating the performance as the electrode of an electrochemical capacitor. The yield after the heat treatment of the carbonization reaction increased by the addition of these flame retardants up to 800 °C. Although both the specific surface area and electrical resistivity are almost independent of the addition of the flame retardants, the capacitance values are improved with the addition of the flame retardants. The nitrogen atoms derived from the flame retardants are introduced to some extent into the synthesized carbon material. Moreover, the phosphorous atoms or the sulfur atoms derived from the flame retardants are doped into the synthesized carbon material. The method applied in this study, that is, the addition of flame retardants before the carbonization process can be used for the doping of the hetero atom such as N, P and S into the carbon material.

  10. Electrochemical sensing platforms based on the different carbon derivative incorporated interface.

    PubMed

    Dervisevic, Muamer; Çevik, Emre; Durmuş, Zehra; Şenel, Mehmet

    2016-01-01

    their effects on the properties of these biosensors. Biosensors were prepared by Horseradish peroxidase (HRP) immobilization on the composite electrodes composed of carbon black, carbon nanofiber (CNF), extended graphite, multiwalled carbon nanotube (MWCNT), reduced graphene oxide (REGO) and poly(glycidyl methacrylateco-vinylferrocene) (P(GMA-co-VFc)) as mediator, covalent linker, and host matrix for carbon derivatives. The modified pencil graphite electrode (PGE) was used for the detection of hydrogen peroxide and to follow electrochemical behavior of different carbon derivatives which were recorded. The electrochemical characterization was investigated by cyclic voltammetry and electrochemical impedance spectroscopy methods. Amperometric measurements showed that the REGO and MWCNT modified electrodes have excellent performance in comparison with other carbon derivatives studied.

  11. Electrochemical synthesis of novel 1,3-indandione derivatives and evaluation of their antiplatelet aggregation activities.

    PubMed

    Amidi, Salimeh; Kobarfard, Farzad; Bayandori Moghaddam, Abdolmajid; Tabib, Kimia; Soleymani, Zohreh

    2013-01-01

    Electrochemical oxidation of some selected catechol derivatives, using cyclic voltammetry, in the presence of different 2-aryl-1,3-indandiones as nucleophiles, resulted in electrochemical synthesis of new 1,3- indandione derivatives in an undivided cell in good yield and purity. A Michael addition mechanism was proposed for the formation of the analogs based on the reaction conditions which were provided in electrochemical cell. The in-vitro antiplatelet and anticoagulant activity of these compounds was evaluated, using arachidonic acid (AA) and adenosine diphosphate (ADP) as the platelet aggregation inducers. The results show that the incorporation of catechol ring in 1,3-indandione nucleus leads to the emergence of antiplatelet aggregation activity in these compounds. The compounds may exert their antiaggregation activity by interfering with the arachidonic acid pathway.

  12. Electrochemical Synthesis of Novel 1,3-Indandione Derivatives and Evaluation of Their Antiplatelet Aggregation Activities

    PubMed Central

    Amidi, Salimeh; Kobarfard, Farzad; Bayandori Moghaddam, Abdolmajid; Tabib, Kimia; Soleymani, Zohreh

    2013-01-01

    Electrochemical oxidation of some selected catechol derivatives, using cyclic voltammetry, in the presence of different 2-aryl-1,3-indandiones as nucleophiles, resulted in electrochemical synthesis of new 1,3- indandione derivatives in an undivided cell in good yield and purity. A Michael addition mechanism was proposed for the formation of the analogs based on the reaction conditions which were provided in electrochemical cell. The in-vitro antiplatelet and anticoagulant activity of these compounds was evaluated, using arachidonic acid (AA) and adenosine diphosphate (ADP) as the platelet aggregation inducers. The results show that the incorporation of catechol ring in 1,3-indandione nucleus leads to the emergence of antiplatelet aggregation activity in these compounds. The compounds may exert their antiaggregation activity by interfering with the arachidonic acid pathway. PMID:24250677

  13. Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

    2014-08-01

    Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

  14. Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

    PubMed Central

    Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

    2014-01-01

    Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

  15. Diamond surface functionalization with biomimicry - Amine surface tether and thiol moiety for electrochemical sensors

    NASA Astrophysics Data System (ADS)

    Sund, James B.; Causey, Corey P.; Wolter, Scott D.; Parker, Charles B.; Stoner, Brian R.; Toone, Eric J.; Glass, Jeffrey T.

    2014-05-01

    The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen-oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis.

  16. Characterization of the Electrochemical Interface by Surface Enhanced Raman Scattering

    NASA Astrophysics Data System (ADS)

    Roy, Dipankar

    The electronic and structural properties of an enhanced raman sensitive interface are investigated. As a model system, the Ag (polycrystalline) electrode/electrolyte interface is chosen. Electrochemical control of the interface is used to establish and influence the conditions for surface enhanced Raman scattering (SERS). The molecule and site specific electronic component of SERS is studied under experimental control. This resonance is responsible for enhancement beyond that caused by electromagnetic effects at the surface and is promoted by the presence of the so -called "SERS active sites" (surface defect sites of atomic scale roughness). The results suggest that, these sites are positively charged, resonant Raman active Ag clusters, most likely with the identity of Ag(,4)('+). A partial contribution to the observed electronic enhancement comes from the intrinsic resonance of the clusters. At a given SERS sensitive Ag electrode, this contribution is superimposed on that from the photon driven charge transfer excitation (CTE) resonance, provided the latter is operative in that particular case. In SERS of Cl('-) (a prototypical probe) on Ag, the internal resonance of Ag(,4)('+) appears to be the primary source of the electronic enhancement detected. By noting the known importance of Ag(,4)('+) in silver-halide photography, it is possible to explain the "photoactivation effect" in SERS in terms of the Ag(,4)('+) identity of SERS active sites. These observations indicate how, by SERS, it may be possible to bridge the gap between the catalytic and optical aspects of small metal clusters. The chemisorbed anions which coexist with the active sites at a SERS sensitive interface, are tested for their effects in SERS from Cl('-) and I('-) on Ag. Evidence is presented for mutual "depolarization" effect of the adsorbates. Under voltage control of these interfaces, this depolarization process dominates the Stark effect and bond perturbation. The results point out how the

  17. In situ electrochemical dilatometry of carbide-derived carbons

    SciTech Connect

    Hantel, M M; Presser, Volker; Gogotsi, Yury

    2011-01-01

    The long life durability and extraordinary stability of supercapacitors are ascribed to the common concept that the charge storage is purely based on double-layer charging. Therefore the ideal supercapacitor electrode should be free of charge induced microscopic structural changes. However, recent in-situ investigations on different carbon materials for supercapacitor electrodes have shown that the charge and discharge is accompanied by dimensional changes of the electrode up to several percent. This work studies the influence of the pore size on the expansion behavior of carbon electrodes derived from titanium carbide-derived carbons with an average pore size between 5 and 8 Using tetraethylammonium tetrafluoroborate in acetonitrile, the swelling of the electrodes was measured by in situ dilatometry. The experiments revealed an increased expansion on the negatively charged electrode for pores below 6 , which could be described with pore swelling.

  18. An electrochemical method for fluoride analysis based on a naphthalene urea derivative as a selective receptor.

    PubMed

    Quintana, Carmen; Suárez, Patricia; Hernández, Lucas

    2008-09-01

    The use of a naphthalene urea derivative as a host molecule for selective fluoride binding allows us to develop a highly selective and sensitive electrochemical method for fluoride analysis without the interference of other halogen atoms. All the parameters affecting the differential pulse voltammetric response of the host molecule used as a fluoride receptor have been optimized and the mechanisms of the electrochemical behavior have been elucidated. The inhibition in the electrochemical signal of the anionic receptor due to the increase of the fluoride amounts allows the determination of F-with an LOD of 3.16 x 10(-6) M with an RSD (%) value lower than 4.8% and an Er (%) value lower than 3.8%.

  19. Electrochemical behavior of bioactive coatings on cp-Ti surface for dental application.

    PubMed

    Marques, Isabella da Silva Vieira; Barão, Valentim Adelino Ricardo; da Cruz, Nilson Cristino; Yuan, Judy Chia-Chun; Mesquita, Marcelo Ferraz; Ricomini-Filho, Antonio Pedro; Sukotjo, Cortino; Mathew, Mathew T

    2015-11-01

    The surface characteristics and electrochemical properties of bioactive coatings produced by plasma electrolytic oxidation (PEO) with calcium, phosphorous, silicon and silver on commercially pure titanium were evaluated. PEO treatment produced a porous oxide layer, which improved the surface topography, and enriched the surface chemistry with bioactive elements, responsible for mimicking bone surface. The surfaces with higher calcium concentration presented antibacterial and biocompability properties with better responses for corrosion and barrier properties, due to the presence of rutile crystalline structure. PEO may be a promising surface treatment option to improve the electrochemical behavior of dental implants mitigating treatment failures.

  20. Carbide-Derived Carbon Films for Integrated Electrochemical Energy Storage

    NASA Astrophysics Data System (ADS)

    Heon, Min

    Active RFID tags, which can communicate over tens or even hundreds of meters, MEMS devices of several microns in size, which are designed for the medical and pharmaceutical purposes, and sensors working in wireless monitoring systems, require microscale power sources that are able to provide enough energy and to satisfy the peak power demands in those applications. Supercapacitors have not been an attractive candidate for micro-scale energy storage, since most nanoporous carbon electrode materials are not compatible with micro-fabrication techniques and have failed to meet the requirements of high volumetric energy density and small form factor for power supplies for integrated circuits or microelectronic devices or sensors. However, supercapacitors can provide high power density, because of fast charging/discharging, which can enable self-sustaining micro-modules when combined with energy-harvesting devices, such as solar cell, piezoelectric or thermoelectric micro-generators. In this study, carbide-derived carbon (CDC) films were synthesized via vacuum decomposition of carbide substrates and gas etching of sputtered carbide thin films. This approach allowed manufacturing of porous carbon films on SiC and silicon substrates. CDC films were studied for micro-supercapacitor electrodes, and showed good double layer capacitance. Since the gas etching technique is compatible with conventional micro-device fabrication processes, it can be implemented to manufacture integrated on-chip supercapacitors on silicon wafers.

  1. Derived Metric Tensors for Flow Surface Visualization.

    PubMed

    Obermaier, H; Joy, K I

    2012-12-01

    Integral flow surfaces constitute a widely used flow visualization tool due to their capability to convey important flow information such as fluid transport, mixing, and domain segmentation. Current flow surface rendering techniques limit their expressiveness, however, by focusing virtually exclusively on displacement visualization, visually neglecting the more complex notion of deformation such as shearing and stretching that is central to the field of continuum mechanics. To incorporate this information into the flow surface visualization and analysis process, we derive a metric tensor field that encodes local surface deformations as induced by the velocity gradient of the underlying flow field. We demonstrate how properties of the resulting metric tensor field are capable of enhancing present surface visualization and generation methods and develop novel surface querying, sampling, and visualization techniques. The provided results show how this step towards unifying classic flow visualization and more advanced concepts from continuum mechanics enables more detailed and improved flow analysis.

  2. Surface Emissivity Derived From Multispectral Satellite Data

    NASA Technical Reports Server (NTRS)

    Minnis, P.; Smith, W. L., Jr.; Young, D. F.

    1998-01-01

    Surface emissivity is critical for remote sensing of surface skin temperature and infrared cloud properties when the observed radiance is influenced by the surface radiation. It is also necessary to correctly compute the longwave flux from a surface at a given skin temperature. Surface emissivity is difficult to determine because skin temperature is an ill-defined parameter. The surface-emitted radiation may arise from a range of surface depths depending on many factors including soil moisture, vegetation, surface porosity, and heat capacity. Emissivity can be measured in the laboratory for pure surfaces. Transfer of laboratory measurements to actual Earth surfaces, however, is fraught with uncertainties because of their complex nature. This paper describes a new empirical approach for estimating surface skin temperature from a combination of brightness temperatures measured at different infrared wavelengths with satellite imagers. The method uses data from the new Geostationary Operational Environmental Satellite (GOES) imager to determine multispectral emissivities from the skin temperatures derived over the ARM Southern Great Plains domain.

  3. Modification of the surface morphology of the silicon substrate for boron-doped diamond electrodes in electrochemical wastewater treatment applications

    NASA Astrophysics Data System (ADS)

    Bak, Ji-Yoon; Lee, Choong-Hyun; Kim, Jung-Do; Lim, Dae-Soon

    2016-01-01

    For electrochemical wastewater treatment applications, textured boron-doped diamond (BDD) electrodes were fabricated by using a simple and cost-effective etching process. On the basis of the surface area measurement, the etching time was optimized in order to achieve higher electrochemical wastewater treatment performance. The surface structure, electrochemical properties, and electrochemical oxidation performance of the electrodes were characterized by using Raman spectroscopy and atomic force microscopy, in addition to electrochemical techniques. The textured BDD electrode demonstrated a dense and large surface area with no change in the film's properties. The effective surface area of the textured BDD electrode was approximately twice as large as that of the planar BDD electrode. The electrochemical results clearly demonstrate that the enhanced surface area of the BDD electrode achieves a higher current efficiency and much lower energy consumption in the electrochemical oxidation of methyl-orange.

  4. Electrochemical and mechanical processes at surfaces and interfaces of advanced materials for energy storage

    NASA Astrophysics Data System (ADS)

    Shi, Feifei

    Energy storage is a rapidly emerging field. In almost all energy storage applications, surfaces and interfaces are playing dominant roles. Examples are fuel cell electrodes, where electro-catalytic reactions occur, Li-ion battery (LIB) electrodes, where electrolyte decomposition and passivation commence simultaneously, and failure (fracture) of battery electrodes, where surface crack initiation greatly affects battery endurance. The most fundamental chemical, electrochemical, and mechanical problems in energy storage applications originate from surfaces and interfaces. This thesis investigates the electrochemical and mechanical processes at surfaces and interfaces of advanced materials for energy applications. The thesis includes the following five main research topics. (Abstract shortened by ProQuest.).

  5. Nanoscale electrochemical patterning reveals the active sites for catechol oxidation at graphite surfaces.

    PubMed

    Patel, Anisha N; McKelvey, Kim; Unwin, Patrick R

    2012-12-19

    Graphite-based electrodes (graphite, graphene, and nanotubes) are used widely in electrochemistry, and there is a long-standing view that graphite step edges are needed to catalyze many reactions, with the basal surface considered to be inert. In the present work, this model was tested directly for the first time using scanning electrochemical cell microscopy reactive patterning and shown to be incorrect. For the electro-oxidation of dopamine as a model process, the reaction rate was measured at high spatial resolution across a surface of highly oriented pyrolytic graphite. Oxidation products left behind in a pattern defined by the scanned electrochemical cell served as surface-site markers, allowing the electrochemical activity to be correlated directly with the graphite structure on the nanoscale. This process produced tens of thousands of electrochemical measurements at different locations across the basal surface, unambiguously revealing it to be highly electrochemically active, with step edges providing no enhanced activity. This new model of graphite electrodes has significant implications for the design of carbon-based biosensors, and the results are additionally important for understanding electrochemical processes on related sp(2)-hybridized materials such as pristine graphene and nanotubes.

  6. Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

    PubMed

    Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

    2016-05-02

    Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

  7. Specific Surface versus Electrochemically Active Area of the Carbon/Polypyrrole Capacitor: Correlation of Ion Dynamics Studied by an Electrochemical Quartz Crystal Microbalance with BET Surface.

    PubMed

    Mosch, Heike L K S; Akintola, Oluseun; Plass, Winfried; Höppener, Stephanie; Schubert, Ulrich S; Ignaszak, Anna

    2016-05-10

    Carbon/polypyrrole (PPy) composites are promising electrode materials for energy storage applications such as lightweight capacitors. Although these materials are composed of relatively inexpensive components, there is a gap of knowledge regarding the correlation between surface, porosity, ion exchange dynamics, and the interplay of the double layer capacitance and pseudocapacitance. In this work we evaluate the specific surface area analyzed by the BET method and the area accessible for ions using electrochemical quartz-crystal microbalance (EQCM) for SWCNT/PPy and carbon black Vulcan XC72-R/PPy composites. The study revealed that the polymer has significant influence on the pore size of the composites. Although the BET surface is low for the polypyrrole, the electrode mass change and thus the electrochemical area are large for the polymer-containing electrodes. This indicates that multiple redox active centers in the charged polymer chain are good ion scavengers. Also, for the composite electrodes, the effective charge storage occurs at the polypyrrole-carbon junctions, which are easy to design/multiply by a proper carbon-to-polymer weight ratio. The specific BET surface and electrochemically accessible surface area are both important parameters in calculation of the electrode capacitance. SWCNTs/PPy showed the highest capacitances normalized to the BET and electrochemical surface as compared to the polymer-carbon black. TEM imaging revealed very homogeneous distribution of the nanosized polymer particles onto the CNTs, which facilitates the synergistic effect of the double layer capacitance (CNTs) and pseudocapacitance (polymer). The trend in the electrode mass change in correlation with the capacitance suggest additional effects such as a solvent co-insertion into the polymer and the contribution of the charge associated with the redox activity of oxygen-containing functional groups on the carbon surface.

  8. Surface working of 304L stainless steel: Impact on microstructure, electrochemical behavior and SCC resistance

    SciTech Connect

    Acharyya, S.G.; Khandelwal, A.; Kain, V.; Kumar, A.; Samajdar, I.

    2012-10-15

    The effect of surface working operations on the microstructure, electrochemical behavior and stress corrosion cracking resistance of 304L stainless steel (SS) was investigated in this study. The material was subjected to (a) solution annealing (b) machining and (c) grinding operations. Microstructural characterization was done using stereo microscopy and electron back scattered diffraction (EBSD) technique. The electrochemical nature of the surfaces in machined, ground and solution annealed condition were studied using potentiodynamic polarization and scanning electrochemical microscopy (SECM) in borate buffer solution. The stress corrosion cracking resistance of 304L SS in different conditions was studied by exposing the samples to boiling MgCl{sub 2} environment. Results revealed that the heavy plastic deformation and residual stresses present near the surface due to machining and grinding operations make 304L SS electrochemically more active and susceptible to stress corrosion cracking. Ground sample showed highest magnitude of current density in the passive potential range followed by machined and solution annealed 304L SS. Micro-electrochemical studies established that surface working promotes localized corrosion along the surface asperities which could lead to crack initiation. - Highlights: Black-Right-Pointing-Pointer Machining/grinding produce extensive grain fragmentation near the surface of 304L SS. Black-Right-Pointing-Pointer Machining/grinding result in martensitic transformation near the surface of 304L SS. Black-Right-Pointing-Pointer Machining/grinding drastically reduce the SCC resistance of 304L SS in chloride. Black-Right-Pointing-Pointer Machining/grinding make the surface of 304L SS electrochemically much more active. Black-Right-Pointing-Pointer SECM study reveal that preferential dissolution takes place along surface asperities.

  9. The electrochemical surface forces apparatus: the effect of surface roughness, electrostatic surface potentials, and anodic oxide growth on interaction forces, and friction between dissimilar surfaces in aqueous solutions.

    PubMed

    Valtiner, Markus; Banquy, Xavier; Kristiansen, Kai; Greene, George W; Israelachvili, Jacob N

    2012-09-11

    We present a newly designed electrochemical surface forces apparatus (EC-SFA) that allows control and measurement of surface potentials and interfacial electrochemical reactions with simultaneous measurement of normal interaction forces (with nN resolution), friction forces (with μN resolution), and distances (with Å resolution) between apposing surfaces. We describe three applications of the developed EC-SFA and discuss the wide-range of potential other applications. In particular, we describe measurements of (1) force-distance profiles between smooth and rough gold surfaces and apposing self-assembled monolayer-covered smooth mica surfaces; (2) the effective changing thickness of anodically growing oxide layers with Å-accuracy on rough and smooth surfaces; and (3) friction forces evolving at a metal-ceramic contact, all as a function of the applied electrochemical potential. Interaction forces between atomically smooth surfaces are well-described using DLVO theory and the Hogg-Healy-Fuerstenau approximation for electric double layer interactions between dissimilar surfaces, which unintuitively predicts the possibility of attractive double layer forces between dissimilar surfaces whose surface potentials have similar sign, and repulsive forces between surfaces whose surface potentials have opposite sign. Surface roughness of the gold electrodes leads to an additional exponentially repulsive force in the force-distance profiles that is qualitatively well described by an extended DLVO model that includes repulsive hydration and steric forces. Comparing the measured thickness of the anodic gold oxide layer and the charge consumed for generating this layer allowed the identification of its chemical structure as a hydrated Au(OH)(3) phase formed at the gold surface at high positive potentials. The EC-SFA allows, for the first time, one to look at complex long-term transient effects of dynamic processes (e.g., relaxation times), which are also reflected in friction

  10. Surface electrochemical control for fine coal and pyrite separation. Technical progress report, July 1, 1991--September 30, 1991

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Li, Jun; Riley, A.; Turcotte, S.B.; Benner, R.E.; Zhu, Ximeng; Bodily, D.M.; Liang, Jun; Zhong, Tinghe; Wadsworth, M.E.

    1991-12-31

    The ongoing work includes the characterization of coal pyrites, the floatability evaluation of three typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces. This report covers a Raman spectroscopy of species produced electrochemically on pyrite surfaces.

  11. Selective electrochemical gold deposition onto p-Si (1 0 0) surfaces

    NASA Astrophysics Data System (ADS)

    Santinacci, L.; Djenizian, T.; Schwaller, P.; Suter, T.; Etcheberry, A.; Schmuki, P.

    2008-09-01

    In this paper, we report selective electrochemical gold deposition onto p-type Si (1 0 0) into nanoscratches produced through a thin oxide layer using an atomic force microscope. A detailed description of the substrate engraving process is presented. The influence of the main scratching parameters such as the normal applied force, the number of scans and the scanning velocity are investigated as well as the mechanical properties of the substrate. Gold deposition is carried out in a KAu(CN)2 + KCN solution by applying cathodic voltages for various durations. The gold deposition process is investigated by cyclic voltammetry. Reactivity enhancement at the scratched locations was studied by comparing the electrochemical behaviour of intact and engraved surfaces using a micro-electrochemical setup. Selective electrochemical gold deposition is achieved: metallic patterns with a sub-500 nm lateral resolution are obtained demonstrating, therefore, the bearing potential of this patterning technique.

  12. Fluorescence Properties and Electrochemical Behavior of Some Schiff Bases Derived from N-Aminopyrimidine.

    PubMed

    Gulcan, Mehmet; Doğru, Ümit; Öztürk, Gülsiye; Levent, Abdulkadir; Akbaş, Esvet

    2014-03-01

    A series of Schiff bases (L 1 , L 2 and L 3) were prepared by refluxing aromatic aldehydes with N-Aminopyrimidine derivatives in methanol and ethanol. The structures of synthesized compounds were characterized by FTIR, (1)H NMR, (13)C NMR and microanalysis. The electrochemical behaviors of the Schiff base ligands were also discussed. Moreover, the evaluation of absorption and emission properties of the structures were carried out in five different solvents. The products show visible absorption maxima in the range of 304-576 nm, and emission maxima from 636 to 736 nm in all solvents tested.

  13. Silicon surface biofunctionalization with dopaminergic tetrahydroisoquinoline derivatives

    NASA Astrophysics Data System (ADS)

    Lucena-Serrano, A.; Lucena-Serrano, C.; Contreras-Cáceres, R.; Díaz, A.; Valpuesta, M.; Cai, C.; López-Romero, J. M.

    2016-01-01

    In this work we grafted vinyl- and azido-terminated tetrahydroisoquinolines (compounds 1 and 2, respectively) onto Hsbnd Si(1 1 1) silicon wafers obtaining highly stable modified surfaces. A double bond was incorporated into the tetrahydroisoquinoline structure of 1 to be immobilized by a light induced hydrosilylation reaction on hydrogen-terminated Si(1 1 1). The best results were obtained employing a polar solvent (DMSO), rather than a non-polar solvent (toluene). The azide derivative 2 was grafted onto alkenyl-terminated silicon substrates with copper-catalyzed azide-alkyne cycloaddition (CuAAC). Atomic force microscopy (AFM), contact angle goniometry (CA) and X-ray photoemission spectroscopy (XPS) were used to demonstrate the incorporation of 1 and 2 into the surfaces, study the morphology of the modified surfaces and to calculate the yield of grafting and surface coverage. CA measurements showed the increase in the surface hydrophobicity when 1 or 2 were incorporated into the surface. Moreover, compounds 1 and 2 were prepared starting from 1-(p-nitrophenyl)tetrahydroisoquinoline 3 under smooth conditions and in good yields. The structures of 1 and 2 were designed with a reduced A-ring, two substituents at positions C-6 and C-7, an N-methyl group and a phenyl moiety at C-1 in order to provide a high affinity against dopaminergic receptors. Moreover, O-demethylation of 1 was carried out once it was adsorbed onto the surface by treatment with BBr3. The method presented constitutes a simple, easily reproducible and high yielding approach for grafting complex organic biomolecules with dopaminergic properties onto silicon surfaces.

  14. Tailoring the surface chemistry of activated carbon cloth by electrochemical methods.

    PubMed

    Tabti, Zakaria; Ruiz-Rosas, Ramiro; Quijada, César; Cazorla-Amorós, Diego; Morallón, Emilia

    2014-07-23

    This paper presents a systematic study of the effect of the electrochemical treatment (galvanostatic electrolysis in a filter-press electrochemical cell) on the surface chemistry and porous texture of commercial activated carbon cloth. The same treatments have been conducted over a granular activated carbon in order to clarify the effect of morphology. The influence of different electrochemical variables, such as the electrode polarity (anodic or cathodic), the applied current (between 0.2 and 1.0 A) and the type of electrolyte (HNO3 and NaCl) have also been analyzed. The anodic treatment of both activated carbons causes an increase in the amount of surface oxygen groups, whereas the cathodic treatment does not produce any relevant modification of the surface chemistry. The HNO3 electrolyte produced a lower generation of oxygen groups than the NaCl one, but differences in the achieved distribution of surface groups can be benefitial to selectively tune the surface chemistry. The porous texture seems to be unaltered after the electro-oxidation treatment. The validity of this method to introduce surface oxygen groups with a pseudocapacitive behavior has been corroborated by cyclic voltammetry. As a conclusion, the electrochemical treatment can be easily implemented to selectively and quantitatively modify the surface chemistry of activated carbons with different shapes and morphologies.

  15. Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

    SciTech Connect

    Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.; Pivovar, Bryan S.

    2016-06-02

    Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparative studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.

  16. Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

    DOE PAGES

    Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.; ...

    2016-06-02

    Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparativemore » studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.« less

  17. Electrochemical CO2 reduction on Cu2O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons.

    PubMed

    Kas, Recep; Kortlever, Ruud; Milbrat, Alexander; Koper, Marc T M; Mul, Guido; Baltrusaitis, Jonas

    2014-06-28

    The catalytic activity and hydrocarbon selectivity in electrochemical carbon dioxide (CO2) reduction on cuprous oxide (Cu2O) derived copper nanoparticles is discussed. Cuprous oxide films with [100], [110] and [111] orientation and variable thickness were electrodeposited by reduction of copper(ii) lactate on commercially available copper plates. After initiation of the electrochemical CO2 reduction by these oxide structures, the selectivity of the process was found to largely depend on the parent Cu2O film thickness, rather than on the initial crystal orientation. Starting with thin Cu2O films, besides CO and hydrogen, selective formation of ethylene is observed with very high ethylene-to-methane ratios (∼8 to 12). In addition to these products, thicker Cu2O films yield a remarkably large amount of ethane. Long term Faradaic efficiency analysis of hydrocarbons shows no sign of deactivation of the electrodes after 5 hours of continuous experiment. Online mass spectroscopy studies combined with X-ray diffraction data suggest the reduction of the Cu2O films in the presence of CO2, generating a nanoparticulate Cu morphology, prior to the production of hydrogen, CO, and hydrocarbons. Optimizing coverage, number density and size of the copper nanoparticles, as well as local surface pH, may allow highly selective formation of the industrially important product ethylene.

  18. An investigation of pyrite depression in coal flotation by electrochemical pyrite surface control

    SciTech Connect

    Zhu Hong; Ou Zeshen; Shi Xiuping; Shen Yanchun

    1995-12-31

    This paper introduces a new potential method of pyrite depression in the flotation of high sulfur coal based on the electrochemical pyrite surface control. Experimental date show that the natural hydrophobicity of pyrite depends on the oxidation-reduction potential of the pulp. The mechanism and products of electrochemical reaction on the pyrite surface are also discussed under various conditions. The pyrite flotation is generally suppressed under low pulp potentials. Therefore, the sulfur removal in the flotation of high sulfur coal could be improved by the pulp redox potential control, while the coal flotation is materially not affected.

  19. Evaluation Of Electrochemical Machining Technology For Surface Improvements In Additive Manufactured Components

    SciTech Connect

    Dehoff, Ryan R.; List, III, Frederick Alyious; Carver, Keith

    2015-09-23

    ORNL Manufacturing Demonstration Facility worked with ECM Technologies LLC to investigate the use of precision electro-chemical machining technology to polish the surface of parts created by Arcam electron beam melting. The goals for phase one of this project have been met. The project goal was to determine whether electro-chemical machining is a viable method to improve the surface finish of Inconel 718 parts fabricated using the Arcam EBM method. The project partner (ECM) demonstrated viability for parts of both simple and complex geometry. During the course of the project, detailed process knowledge was generated. This project has resulted in the expansion of United States operations for ECM Technologies.

  20. Friction Reduction of Chrome-Coated Surface with Micro-Dimple Arrays Generated by Electrochemical Micromachining

    NASA Astrophysics Data System (ADS)

    Chen, Xiaolei; Qu, Ningsong; Hou, Zhibao; Wang, Xiaolei; Zhu, Di

    2017-02-01

    Surface coating and surface texture play a significant role in enhancing the tribological properties of mechanical components. In this study, to further improve the tribological properties of a chrome-coated surface, arrays of circular- and square-shaped micro-dimples were generated on chrome-coated surfaces via electrochemical machining. Through-mask electrochemical micromachining (TMEMM) is a popular electrochemical micromachining method for generating micro-dimple arrays. However, photolithography is a necessary process in conventional TMEMM before electrochemical micromachining, which is time-consuming and expensive when used in mass production. A reusable polydimethylsiloxane mask was introduced to prepare the micro-dimples. Circular micro-dimples of 120 μm diameter and square micro-dimples of 106 μm side length were fabricated on a chrome-coated surface. The results of friction tests indicated that at a load of 220 N, 10 μm deep micro-dimples reduced the coefficient of friction (CoF) significantly compared to an untextured surface. At a load of 320 and 420 N, the CoF continually decreased when the depth of the micro-dimples was increased from 0 to 20 μm. In addition, the results showed that, compared to circular micro-dimples, square micro-dimples contributed to a higher friction reduction ratio under the same conditions. The best friction reduction ratio was found for square dimples with a depth of 20 μm.

  1. Friction Reduction of Chrome-Coated Surface with Micro-Dimple Arrays Generated by Electrochemical Micromachining

    NASA Astrophysics Data System (ADS)

    Chen, Xiaolei; Qu, Ningsong; Hou, Zhibao; Wang, Xiaolei; Zhu, Di

    2017-01-01

    Surface coating and surface texture play a significant role in enhancing the tribological properties of mechanical components. In this study, to further improve the tribological properties of a chrome-coated surface, arrays of circular- and square-shaped micro-dimples were generated on chrome-coated surfaces via electrochemical machining. Through-mask electrochemical micromachining (TMEMM) is a popular electrochemical micromachining method for generating micro-dimple arrays. However, photolithography is a necessary process in conventional TMEMM before electrochemical micromachining, which is time-consuming and expensive when used in mass production. A reusable polydimethylsiloxane mask was introduced to prepare the micro-dimples. Circular micro-dimples of 120 μm diameter and square micro-dimples of 106 μm side length were fabricated on a chrome-coated surface. The results of friction tests indicated that at a load of 220 N, 10 μm deep micro-dimples reduced the coefficient of friction (CoF) significantly compared to an untextured surface. At a load of 320 and 420 N, the CoF continually decreased when the depth of the micro-dimples was increased from 0 to 20 μm. In addition, the results showed that, compared to circular micro-dimples, square micro-dimples contributed to a higher friction reduction ratio under the same conditions. The best friction reduction ratio was found for square dimples with a depth of 20 μm.

  2. Quinoxaline derivatives as corrosion inhibitors for mild steel in hydrochloric acid medium: Electrochemical and quantum chemical studies

    NASA Astrophysics Data System (ADS)

    Olasunkanmi, Lukman O.; Kabanda, Mwadham M.; Ebenso, Eno E.

    2016-02-01

    The corrosion inhibition potential of four quinoxaline derivatives namely, 1-[3-(4-methylphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]butan-1-one (Me-4-PQPB), 1-(3-(4-methoxyphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl)butan-1-one (Mt-4-PQPB), 1-[3-(3-methoxyphenyl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]butan-1-one (Mt-3-PQPB) and 1-[3-(2H-1,3-benzodioxol-5-yl)-5-(quinoxalin-6-yl)-4,5-dihydropyrazol-1-yl]butan-1-one (Oxo-1,3-PQPB) was studied for mild steel corrosion in 1 M HCl solution using electrochemical, spectroscopic techniques and quantum chemical calculations. The results of both potentiodynamic polarization and electrochemical impedance spectroscopic studies revealed that the compounds are mixed-type inhibitors and the order of corrosion inhibition efficiency at 100 ppm is Me-4-PQPB>Mt-3-PQPB>Oxo-1,3-PQPB>Mt-4-PQPB. Fourier transform infrared (FTIR) and ultraviolet-visible (UV-vis) spectroscopic analyses confirmed the presence of chemical interactions between the inhibitors and mild steel surface. The adsorption of the inhibitor molecules on mild steel surface was found to be both physisorption and chemisorption but predominantly chemisorption. The experimental data obey Langmuir adsorption isotherm. Scanning electron microscopy studies revealed the formation of protective films of the inhibitors on mild steel surface. Quantum chemical parameters obtained from density functional theory (DFT) calculations support experimental results.

  3. Effects of CO2 activation on electrochemical performance of microporous carbons derived from poly(vinylidene fluoride)

    NASA Astrophysics Data System (ADS)

    Lee, Seul-Yi; Park, Soo-Jin

    2013-11-01

    In this work, we have prepared microporous carbons (MPCs) derived from poly(vinylidene fluoride) (PVDF), and the physical activation of MPCs using CO2 gas is subsequently carried out with various activation temperatures to investigate the electrochemical performance. PVDF is successfully converted into MPCs with a high specific surface area and well-developed micropores. After CO2 activation, the specific surface areas of MPCs (CA-MPCs) are enhanced by 12% compared with non-activated MPCs. With increasing activation temperature, the micropore size distributions of A-MPCs also become narrower and shift to larger pore size. It is also confirmed that the CO2 activation had developed the micropores and introduced the oxygen-containing groups to MPCs‧ surfaces. From the results, the specific capacitances of the electrodes in electric double layer capacitors (EDLCs) based on CA-MPCs are distinctly improved through CO2 activation. The highest specific capacitance of the A-MPCs activated at 700 °C is about 125 F/g, an enhancement of 74% in comparison with NA-MPCs, at a discharge current of 2 A/g in a 6 M KOH electrolyte solution. We also found that micropore size of 0.67 nm has a specific impact on the capacitance behaviors, besides the specific surface area of the electrode samples.

  4. Improving electrochemical properties of AISI 1045 steels by duplex surface treatment of plasma nitriding and aluminizing

    NASA Astrophysics Data System (ADS)

    Haftlang, Farahnaz; Habibolahzadeh, Ali; Sohi, Mahmoud Heydarzadeh

    2015-02-01

    Improvement in electrochemical behavior of AISI 1045 steel after applying aluminum nitride coating was investigated in 3.5% NaCl solution, using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) analyses. Aluminum nitride coating was applied on the steel surface by duplex treatment of pack aluminizing and plasma nitriding. Some specimens were plasma nitrided followed by aluminizing (PN-Al), while the others were pack aluminized followed by plasma nitriding (Al-PN). Topological and structural studies of the modified surfaces were conducted using scanning electron microscope (SEM) equipped by energy dispersive X-ray spectroscope (EDS), and X-ray diffractometer (XRD). The electrochemical measurements showed that the highest corrosion and polarization (Rp) resistances were obtained in PN-Al specimens, having single phase superficial layer of AlN. Pitting mechanism was dominant reason of lower corrosion resistance in the Al-PN specimens.

  5. Synthesis, characterization, and electrochemical applications of carbon nanoparticles derived from castor oil soot.

    PubMed

    Prasad, K Sudhakara; Chuang, Min-Chieh; Ho, Ja-An Annie

    2012-01-15

    A simple procedure for the modification of carbon nanoparticles (CNPs) from castor oil soot using acid treatment was described herein. Characterization studies revealed the presence of edge plane sites and surface carbon-oxygen functionalities at the surface of the CNP material. Voltammetric studies revealed the increased electrochemical activity of the CNP-modified electrode toward various biologically important molecules, including dopamine, uric acid, dihydronicotinamide adenine dinucleotide, tyrosine, and serotonin, relative to those obtained using the unmodified electrode. The improved electro-oxidation potentials for these compounds-and, thereby, the enhanced sensitivity of related sensors-was due directly to the presence of surface C(δ+)O(δ-) functional groups and the greater number of edge plane sites developed after acid treatment of the soot sample.

  6. Superwetting and aptamer functionalized shrink-induced high surface area electrochemical sensors.

    PubMed

    Hauke, A; Kumar, L S Selva; Kim, M Y; Pegan, J; Khine, M; Li, H; Plaxco, K W; Heikenfeld, J

    2017-03-12

    Electrochemical sensing is moving to the forefront of point-of-care and wearable molecular sensing technologies due to the ability to miniaturize the required equipment, a critical advantage over optical methods in this field. Electrochemical sensors that employ roughness to increase their microscopic surface area offer a strategy to combatting the loss in signal associated with the loss of macroscopic surface area upon miniaturization. A simple, low-cost method of creating such roughness has emerged with the development of shrink-induced high surface area electrodes. Building on this approach, we demonstrate here a greater than 12-fold enhancement in electrochemically active surface area over conventional electrodes of equivalent on-chip footprint areas. This two-fold improvement on previous performance is obtained via the creation of a superwetting surface condition facilitated by a dissolvable polymer coating. As a test bed to illustrate the utility of this approach, we further show that electrochemical aptamer-based sensors exhibit exceptional signal strength (signal-to-noise) and excellent signal gain (relative change in signal upon target binding) when deployed on these shrink electrodes. Indeed, the observed 330% gain we observe for a kanamycin sensor is 2-fold greater than that seen on planar gold electrodes.

  7. Electrochemical and spectroscopic characterization of surface sol-gel processes.

    PubMed

    Chen, Xiaohong; Wilson, George S

    2004-09-28

    (3-Mercaptopropyl)trimethoxysilane (MTS) forms a unique film on a platinum substrate by self-assembly and sol-gel cross-linking. The gelating and drying states of the self-assembled MTS sol-gel films were probed by use of electrochemical and spectroscopic methods. The thiol moiety was the only active group within the sol-gel network. Gold nanoparticles were employed to detect the availability of the thiol group and their interaction further indicated the physicochemical states of the sol-gel inner structure. It was found that the thiol groups in the open porous MTS aerogel matrix were accessible to the gold nanoparticles while thiol groups in the compact MTS xerogel network were not accessible to the gold nanoparticles. The characteristics of the sol-gel matrix change with time because of its own irreversible gelating and drying process. The present work provides direct evidence of gold nanoparticle binding with thiol groups within the sol-gel structures and explains the different permeability of "aerogel" and "xerogel" films of MTS on the basis of electrochemical and spectroscopic results. Two endogenous species, hydrogen peroxide and ascorbic acid, were used to test the permeability of the self-assembled sol-gel film in different states. The MTS xerogel film on the platinum electrode was extremely selective against ascorbic acid while maintaining high sensitivity to hydrogen peroxide in contrast to the relatively high permeability of ascorbic acid in the MTS aerogel film. This study showed the potential of the MTS sol-gel film as a nanoporous material in biosensor development.

  8. Surface structured platinum electrodes for the electrochemical reduction of carbon dioxide in imidazolium based ionic liquids.

    PubMed

    Hanc-Scherer, Florin A; Montiel, Miguel A; Montiel, Vicente; Herrero, Enrique; Sánchez-Sánchez, Carlos M

    2015-10-07

    The direct CO2 electrochemical reduction on model platinum single crystal electrodes Pt(hkl) is studied in [C2mim(+)][NTf2(-)], a suitable room temperature ionic liquid (RTIL) medium due to its moderate viscosity, high CO2 solubility and conductivity. Single crystal electrodes represent the most convenient type of surface structured electrodes for studying the impact of RTIL ion adsorption on relevant electrocatalytic reactions, such as surface sensitive electrochemical CO2 reduction. We propose here based on cyclic voltammetry and in situ electrolysis measurements, for the first time, the formation of a stable adduct [C2mimH-CO2(-)] by a radical-radical coupling after the simultaneous reduction of CO2 and [C2mim(+)]. It means between the CO2 radical anion and the radical formed from the reduction of the cation [C2mim(+)] before forming the corresponding electrogenerated carbene. This is confirmed by the voltammetric study of a model imidazolium-2-carboxylate compound formed following the carbene pathway. The formation of that stable adduct [C2mimH-CO2(-)] blocks CO2 reduction after a single electron transfer and inhibits CO2 and imidazolium dimerization reactions. However, the electrochemical reduction of CO2 under those conditions provokes the electrochemical cathodic degradation of the imidazolium based RTIL. This important limitation in CO2 recycling by direct electrochemical reduction is overcome by adding a strong acid, [H(+)][NTf2(-)], into solution. Then, protons become preferentially adsorbed on the electrode surface by displacing the imidazolium cations and inhibiting their electrochemical reduction. This fact allows the surface sensitive electro-synthesis of HCOOH from CO2 reduction in [C2mim(+)][NTf2(-)], with Pt(110) being the most active electrode studied.

  9. A silk derived carbon fiber mat modified with Au@Pt urchilike nanoparticles: A new platform as electrochemical microbial biosensor.

    PubMed

    Deng, Liu; Guo, Shaojun; Zhou, Ming; Liu, Ling; Liu, Chang; Dong, Shaojun

    2010-06-15

    We present here a facile and efficient route to prepare silk derived carbon mat modified with Au@Pt urchilike nanoparticles (Au@Pt NPs) and develop an Escherichia coli (E. coli)-based electrochemical sensor using this material. Silk is a natural protein fiber, and it is abundant with kinds of functionalities which are important in the development of the derived material. The S-derived carbon fiber mat have amino, pyridine and carbonyl functional groups, these natural existent functionalities allow the Au@Pt NPs to self-assemble on the carbon fiber surface and provide a biocompatible microenvironment for bacteria. The Au@Pt NPs modified S-derived carbon fiber is sensitive to detect the E. coli activities with a low detection limit, where glucose is used as a prelimiltary substrate to evaluate them. The performance of Au@Pt/carbon fiber mat based biosensor is much better than that of commercial carbon paper based biosensor. The high sensitivity of this biosensor stems from the unique electrocatalytic properties of Au@Pt urchilike NPs and quinone groups presented in S-derived carbon fiber. This biosensor is also tested for detection of organophosphate pesticides, fenamiphos. The relative inhibition of E. coli activity is linear with -log[fenamiphos] at the concentration range from 0.5mg/L to 36.6 mg/L with lowest observable effect concentration (LOEC) of 0.09 mg/L. The Au@Pt NPs modified S-derived carbon fiber mat possesses high conductivity, biocompatibility and high electrocatalytic activity and be can used as advanced electrode materials for microbial biosensor improvement. The microbial biosensor based on this material shows potential applications in environmental monitoring.

  10. Surface electrochemical control for fine coal and pyrite separation. Technical progress report, October 1, 1991--December 31, 1991

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Li, Jun; Zhu, Ximeng; Bodily, D.M.; Liang, Jun; Zhong, Tingke; Wadsworth, M.E.

    1991-12-31

    The ongoing work includes the characterization of coal pyrites, the floatability evaluation of three typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces. This report contains three sections, ``Transpassive Oxidation of Pyrite,`` ``Flotation and Electrochemical Pretreatment,`` and ``Flotation Kinetics of Coal and Coal Pyrite.``

  11. Surface design and engineering of hierarchical hybrid nanostructures for asymmetric supercapacitors with improved electrochemical performance.

    PubMed

    Achilleos, Demetra S; Hatton, T Alan

    2015-06-01

    With the current rising world demand for energy sufficiency, there is an increased necessity for the development of efficient energy storage devices. To address these needs, the scientific community has focused on the improvement of the electrochemical properties of the most well known energy storage devices; the Li-ion batteries and electrochemical capacitors, also called supercapacitors. Despite the fact that supercapacitors exhibit high power densities, good reversibility and long cycle life, they still exhibit lower energy densities than batteries, which limit their practical application. Various strategies have been employed to circumvent this problem, specifically targetting an increase in the specific capacitance and the broadening of the potential window of operation of these systems. In recent years, sophisticated surface design and engineering of hierarchical hybrid nanostructures has facilitated significant improvements in the specific and volumetric storage capabilities of supercapacitors. These nanostructured electrodes exhibit higher surface areas for ion adsorption and reduced ion diffusion lengths for the electrolyte ions. Significant advances have also been achieved in broadening the electrochemical window of operation of these systems, as realized via the development of asymmetric two-electrode cells consisting of nanocomposite positive and negative electrodes with complementary electrochemical windows, which operate in environmentally benign aqueous media. We provide an overview of the diverse approaches, in terms of chemistry and nanoscale architecture, employed recently for the development of asymmetric supercapacitors of improved electrochemical performance.

  12. Electrochemical surface plasmon resonance biosensor for study of DNA desorption and hybridization

    NASA Astrophysics Data System (ADS)

    Ferrari, Luca; Šípová, Hana; Tichý, Ivo; Chadt, Karel; Homola, Jiri

    2013-05-01

    We report a system, which combines electrochemical and surface plasmon resonance (SPR) techniques on the same sensing chip. Each channel of a four-channel laboratory SPR sensor is supplemented with two planar gold electrodes (the reference and the counter electrodes), whereas the gold layer of SPR chip is used as the working electrode. A custom electronics enables to set an arbitrary potential between the reference and working electrodes and to measure the current flow between the counter and the working electrodes. Information from standard electrochemical techniques, i.e. cyclovoltammetry and chronoamperometry can be acquired with the system while simultaneously monitoring the shift in the surface plasmon resonance. The electrochemical SPR biosensor was used to study desorption of thiolated DNA probes with a negative potential. By comparing the acquired electrochemical and SPR signals, we show that DNA probes as well as a monolayer of alkanethiols can be desorbed by applying negative potentials to the SPR chip surface. Moreover, it is shown that the DNA probes can be reabsorbed on the SPR sensor surface and the complementary DNA can be detected without loss in detection sensitivity.

  13. Fabrication of microlens array on silicon surface using electrochemical wet stamping technique

    NASA Astrophysics Data System (ADS)

    Lai, Lei-Jie; Zhou, Hang; Zhu, Li-Min

    2016-02-01

    This paper focuses on the fabrication of microlens array (MLA) on silicon surface by taking advantage of a novel micromachining approach, the electrochemical we stamping (E-WETS). The E-WETS allows the direct imprinting of MLA on an agarose stamp into the substrate through a selective anodic dissolution process. The pre-patterned agarose stamp can direct and supply the solution preferentially on the contact area between the agarose stamp and the substrate, to which the electrochemical reaction is confined. The anodic potential vs. saturated calomel electrode is optimized and 1.5 V is chosen as the optimum value for the electrochemical polishing of p-Si. A refractive MLA on a PMMA mold is successfully transferred onto the p-Si surface. The machining deviations of the fabricated MLA from those on the mold are 0.44% in diameter and 2.1% in height respectively, and the machining rate in HF is around 1.1 μm/h. The surface roughness of the fabricated MLA is less than 12 nm owing to the electrochemical polishing process. The results demonstrate that E-WETS is a promising approach to fabricate MLA on p-Si surface with high accuracy and efficiency.

  14. Wide electrochemical window of supercapacitors from coffee bean-derived phosphorus-rich carbons.

    PubMed

    Huang, Congcong; Sun, Ting; Hulicova-Jurcakova, Denisa

    2013-12-01

    Phosphorus-rich carbons (PCs) were prepared by phosphoric acid activation of waste coffee grounds in different impregnation ratios. PCs were characterized by nitrogen and carbon dioxide adsorption and X-ray photoelectron spectroscopy. The results indicate that the activation step not only creates a porous structure, but also introduces various phosphorus and oxygen functional groups to the surface of carbons. As evidenced by cyclic voltammetry, galvanostatic charge/discharge, and wide potential window tests, a supercapacitor constructed from PC-2 (impregnation ratio of 2), with the highest phosphorus content, can operate very stably in 1 M H2 SO4 at 1.5 V with only 18 % degradation after 10 000 cycles at a current density of 5 A g(-1) . Due to the wide electrochemical window, a supercapacitor assembled with PC-2 has a high energy density of 15 Wh kg(-1) at a power density of 75 W kg(-1) . The possibility of widening the potential window above the theoretical potential for the decomposition of water is attributed to reversible electrochemical hydrogen storage in narrow micropores and the positive effect of phosphorus-rich functional groups, particularly the polyphosphates on the carbon surface.

  15. Electrochemical Deposition of Niobium onto the Surface of Copper Using a Novel Choline Chloride-Based Ionic Liquid

    SciTech Connect

    Wixtroma, Alex I.; Buhlera, Jessica E.; Reece, Charles E.; Abdel-Fattah, Tarek M.

    2013-06-01

    Recent research has shown that choline chloride-based solutions can be used to replace acid-based electrochemical polishing solutions. In this study niobium metal was successfully deposited on the surface of copper substrate via electrochemical deposition using a novel choline chloride-based ionic liquid. The niobium metal used for deposition on the Cu had been dissolved in the solution from electrochemical polishing of a solid niobium piece prior to the deposition. The visible coating on the surface of the Cu was analyzed using scanning electron microscopy (SEM) and electron dispersive x-ray spectroscopy (EDX). This deposition method effectively recycles previously dissolved niobium from electrochemical polishing.

  16. Surface electrochemical control for fine coal and pyrite separation. Technical progress report, April 1, 1990--June 30, 1990

    SciTech Connect

    Hu, Weibai; Zhu, Ximeng; Bodily, D.M.; Wadsworth, M.E.

    1990-12-31

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  17. Electrochemical Interrogation of Interactions between Surface-Confined DNA and Methylene Blue

    PubMed Central

    Pan, Dun; Zuo, Xiaolei; Wan, Ying; Wang, Lihua; Zhang, Jiong; Song, Shiping; Fan, Chunhai

    2007-01-01

    In this work, we reported a systematic investigation on the interactions between methylene blue (MB) and surface-confined DNA by using electrochemical methods. We demonstrated that the redox potential of MB and binding and dissociation kinetics of MB to DNA differed significantly for single-stranded DNA (ss-DNA) and double-stranded DNA (ds-DNA) immobilized on gold electrodes. This was possibly due to the different binding mechanism between MB and ss- or ds-DNA. This work might provide useful information for developing MB-based sequence-specific electrochemical DNA sensors.

  18. Electrochemical and theoretical analysis of the reactivity of shikonin derivatives: dissociative electron transfer in esterified compounds.

    PubMed

    Armendáriz-Vidales, Georgina; Frontana, Carlos

    2014-09-07

    An electrochemical and theoretical analysis of a series of shikonin derivatives in aprotic media is presented. Results showed that the first electrochemical reduction signal is a reversible monoelectronic transfer, generating a stable semiquinone intermediate; the corresponding E(I)⁰ values were correlated with calculated values of electroaccepting power (ω(+)) and adiabatic electron affinities (A(Ad)), obtained with BH and HLYP/6-311++G(2d,2p) and considering the solvent effect, revealing the influence of intramolecular hydrogen bonding and the substituting group at position C-2 in the experimental reduction potential. For the second reduction step, esterified compounds isobutyryl and isovalerylshikonin presented a coupled chemical reaction following dianion formation. Analysis of the variation of the dimensionless cathodic peak potential values (ξ(p)) as a function of the scan rate (v) functions and complementary experiments in benzonitrile suggested that this process follows a dissociative electron transfer, in which the rate of heterogeneous electron transfer is slow (~0.2 cm s(-1)), and the rate constant of the chemical process is at least 10(5) larger.

  19. [Surface science instrumentation for the study of important catalytic and electrochemical interfaces

    SciTech Connect

    Not Available

    1992-01-01

    The equipment combines several standard surface science probes (uv photoelectron spectra, thermal desorption, AES) with a state-of-the art x-ray photoelectron spectrometer and integrates with a dry box and a custom electrochemical cell. After the LEED chamber was remachined, the instrument has been performing satisfactorily. Various studies using the instrument were conducted in cooperation with other groups. Si surfaces were studied before and after use as a photoanode in a photoelectrochemical cell.

  20. [Surface science instrumentation for the study of important catalytic and electrochemical interfaces]. Annual technical report

    SciTech Connect

    Not Available

    1992-12-31

    The equipment combines several standard surface science probes (uv photoelectron spectra, thermal desorption, AES) with a state-of-the art x-ray photoelectron spectrometer and integrates with a dry box and a custom electrochemical cell. After the LEED chamber was remachined, the instrument has been performing satisfactorily. Various studies using the instrument were conducted in cooperation with other groups. Si surfaces were studied before and after use as a photoanode in a photoelectrochemical cell.

  1. Electrochemically induced reconstruction of the Au(001) surface: An x-ray scattering study

    SciTech Connect

    Ocko, B.M.; Wang, Jia.

    1991-01-01

    In-situ x-ray specular reflectivity and glancing incident angle x-ray diffraction measurements have been performed in the Au(001) surface in two solutions under potential control in an electrochemical cell. In both the 0.01 M HCl0{sub 4} and 0.01 M KBr solutions a (5 {times} 20)'' reconstruction is formed at sufficient negative potentials. The reconstruction is similar to that obtained for the clean surface in vacuum.

  2. Electrochemically induced reconstruction of the Au(001) surface: An x-ray scattering study

    SciTech Connect

    Ocko, B.M.; Wang, Jia

    1991-12-31

    In-situ x-ray specular reflectivity and glancing incident angle x-ray diffraction measurements have been performed in the Au(001) surface in two solutions under potential control in an electrochemical cell. In both the 0.01 M HCl0{sub 4} and 0.01 M KBr solutions a ``(5 {times} 20)`` reconstruction is formed at sufficient negative potentials. The reconstruction is similar to that obtained for the clean surface in vacuum.

  3. Electrochemical treatment of deproteinated whey wastewater and optimization of treatment conditions with response surface methodology.

    PubMed

    Güven, Güray; Perendeci, Altunay; Tanyolaç, Abdurrahman

    2008-08-30

    Electrochemical treatment of deproteinated whey wastewater produced during cheese manufacture was studied as an alternative treatment method for the first time in literature. Through the preliminary batch runs, appropriate electrode material was determined as iron due to high removal efficiency of chemical oxygen demand (COD), and turbidity. The electrochemical treatment conditions were optimized through response surface methodology (RSM), where applied voltage was kept in the range, electrolyte concentration was minimized, waste concentration and COD removal percent were maximized at 25 degrees C. Optimum conditions at 25 degrees C were estimated through RSM as 11.29 V applied voltage, 100% waste concentration (containing 40 g/L lactose) and 19.87 g/L electrolyte concentration to achieve 29.27% COD removal. However, highest COD removal through the set of runs was found as 53.32% within 8h. These results reveal the applicability of electrochemical treatment to the deproteinated whey wastewater as an alternative advanced wastewater treatment method.

  4. Colonization of Bacteria on the Surfaces of Cold-Sprayed Copper Coatings Alters Their Electrochemical Behaviors

    NASA Astrophysics Data System (ADS)

    Suo, Xinkun; Abdoli, Leila; Liu, Yi; Xia, Peng; Yang, Guanjun; Li, Hua

    2017-02-01

    Copper coatings were fabricated on stainless steel plates by cold spraying. Attachment and colonization of Bacillus sp. on their surfaces in artificial seawater were characterized, and their effects on anticorrosion performances of the coatings were examined. Attached bacteria were observed using field emission scanning electron microscopy. Electrochemical behaviors including potentiodynamic polarization and electrochemical impedance spectroscopy with/without bacterial attachment were evaluated using commercial electrochemical analysis station Modulab. Results show that Bacillus sp. opt to settle on low-lying spots of the coating surfaces in early stage, followed by recruitment and attachment of extracellular polymeric substances (EPS) secreted through metabolism of Bacillus sp. The bacteria survive with the protection of EPS. An attachment model is proposed to illustrate the bacterial behaviors on the surfaces of the coatings. Electrochemical data show that current density under Bacillus sp. environment decreases compared to that without the bacteria. Charge-transfer resistance increases markedly in bacteria-containing seawater, suggesting that corrosion resistance increases and corrosion rate decreases. The influencing mechanism of bacteria settlement on corrosion resistance of the cold-sprayed copper coatings was discussed and elucidated.

  5. Electrochemically-Controlled Compositional Oscillations of Oxide Surfaces

    SciTech Connect

    Mutoro, Eva; Crumlin, Ethan; Pöpke, Hendrik; Luerssen, Bjoern; Amati, Matteo; Abyaneh, Majid; Biegalski, Michael D; Christen, Hans M; Gregoratti, Luca; Janek, Jürgen; Shao-Horn, Yang

    2012-01-01

    Perovskite oxides can exhibit a wide range of interesting characteristics such as being catalytically active and electronically and/or ionically conducting, and thus they have been used in a number of solid-state devices such as solid oxide fuel cells and sensors. As the surface compositions of perovskites can greatly influence the catalytic properties, knowing and controlling their surface chemistries is crucial to enhance device performance. In this study, we demonstrate that the surface strontium (Sr) and cobalt (Co) concentrations of perovskite-based thin films can be controlled reversibly at elevated temperatures by applying small electrical potential biases. The surface chemistry changes of La0.8Sr0.2CoO3 (LSC113), LaSrCoO4 (LSC214), and LSC214-decorated LSC113 films (LSC113/214) were investigated in situ by utilizing synchrotron-based X-ray photoelectron spectroscopy (XPS), where the largest changes of surface Sr was found for the LSC113/214 surface. These findings offer the potential of reversibly controlling the surface functionality of perovskites.

  6. Novel sensory surface for creatine kinase electrochemical detection.

    PubMed

    Moreira, Felismina T C; Dutra, Rosa A F; Noronha, João P; Sales, M Goreti F

    2014-06-15

    This work describes a novel concept of biosensor for quantifying enzymes, where the substrate is immobilized directly over the working area of a screen printed electrode (Au-SPE). This concept is applied here to creatine kinase isoenzyme (CK-MB), a cardiac biomarker in ischemic conditions. It acts as a phospho-transferase on creatine (Crea), requiring the presence of phosphate. So, the phosphorylated form of creatine (Pcrea) was immobilized on the Au/SPE previously aminated with cysteamine (Cys) by self-assembling monolayer technique. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) studies were used to follow the chemical modifications in the Au-SPE. Since Pcrea is an electroactive species at low potential, its consumption over the platform by the enzyme changed the electrical response of the biosensor. So, CK-MB determination has been achieved in mediator free-conditions due the redox proprieties of the Pcrea. The analytical features of the resulting biosensor were studied by square wave voltammetry (SWV). The limit of detection was 0.11 µg/mL and the slope was -0.029(± 0.0035) µA × mL/µg. The interference effect of troponin T (TnT), bovine serum albumin (BSA) and myoglobin (Myo) in the performance of the sensor was tested and good selectivity was observed. The biosensor was successfully applied to biological fluids, showing good stability at room temperature and excellent sensitivity and selectivity. This new concept of biosensor is especially useful for point of care (POC) applications, due to the low cost and small size of the final device.

  7. Interactions at the mild steel acid solution interface in the presence of O-fumaryl-chitosan: Electrochemical and surface studies.

    PubMed

    Sangeetha, Y; Meenakshi, S; Sundaram, C Sairam

    2016-01-20

    The performance of synthesised O-fumaryl-chitosan (OFC) as corrosion inhibitor for mild steel in 1M HCl has been evaluated through various studies. The initial screening by weight loss method revealed the good inhibition efficiency by the inhibitor. Thermodynamic and kinetic parameters have been calculated and discussed. The mode of adsorption is physical in nature and it follows Langmuir adsorption isotherm. Electrochemical measurements supported the inhibition of mild steel by the fumaryl derivative of chitosan. Polarisation studies provided the information that the inhibition is of mixed type. The formation of inhibitor film is assured by surface morphological studies with Scanning electron microscopy (SEM) and Atomic force microscopy (AFM). The mechanism of inhibition is derived from the Fourier-transform infrared (FTIR) spectroscopy and zero charge potential measurement. The adsorbed film is characterised using FTIR and X-ray diffraction studies (XRD).

  8. Elastomers bonded to metal surfaces seal electrochemical cells

    NASA Technical Reports Server (NTRS)

    Sherfey, J. M.

    1964-01-01

    A leakproof seal secondary cell containing alkaline electrolytes was developed by bonding an alkali-resistant elastomer, such as neoprene, to metal contact surfaces. Test results of several different elastomers strongly indicate the feasibility of this sealing method.

  9. Synthesis and electrochemical properties of niobium pentoxide deposited on layered carbide-derived carbon

    NASA Astrophysics Data System (ADS)

    Zhang, Chuanfang (John); Maloney, Ryan; Lukatskaya, Maria R.; Beidaghi, Majid; Dyatkin, Boris; Perre, Emilie; Long, Donghui; Qiao, Wenming; Dunn, Bruce; Gogotsi, Yury

    2015-01-01

    Herein we report on the hydrothermal synthesis of niobium pentoxide on carbide-derived carbon (Nb2O5/CDC) with a layered structure. The presence of phenylphosphonic acid guides the deposition during preparation, leading to the formation of amorphous Nb2O5 particles which are 4-10 nm in diameter and homogeneously distributed on the CDC framework. Electrochemical testing of the Nb2O5/CDC electrode indicated that the highest capacitance and Coulombic efficiency occurred using an electrolyte comprised of 1 M lithium perchlorate in ethylene carbonate/dimethyl carbonate. Subsequent heat treatment of Nb2O5/CDC in CO2 environment led to crystallization of the Nb2O5, allowing reversible Li+ intercalation/de-intercalation. For sweep rates corresponding to charging and discharging in under 3 min, a volumetric charge of 180 C cm-3 and Coulombic efficiency of 99.2% were attained.

  10. Role of precursor crystal structure on electrochemical performance of carbide-derived carbon electrodes

    NASA Astrophysics Data System (ADS)

    Palazzo, Benjamin; Norris, Zach; Taylor, Greg; Yu, Lei; Lofland, Samuel; Hettinger, Jeffrey

    2015-03-01

    Binary carbides with hexagonal and cubic crystal structures have been synthesized by reactive magnetron sputtering of vanadium and other transition metals in acetylene or methane gas mixed with argon. The binary carbides are converted to carbide-derived carbon (CDC) films using chlorine gas in a post-deposition process in an external vacuum reaction furnace. Residual chlorine has been removed using an annealing step in a hydrogen atmosphere. The CDC materials have been characterized by x-ray diffraction, x-ray fluorescence, and scanning electron microscopy. The performance of the CDC materials in electrochemical device applications has been measured with the hexagonal phase precursor demonstrating a significantly higher specific capacitance in comparison to that of the cubic phase. We report these results and pore-size distributions of these and similar materials.

  11. Electrochemical assay for determining nitrosyl derivatives of human hemoglobin: nitrosylhemoglobin and S-nitrosylhemoglobin.

    PubMed

    Palmerini, Carlo A; Arienti, Giuseppe; Palombari, Roberto

    2004-07-15

    Nitric oxide (NO) is an important biological regulator. It can bind to heme iron and form NO+, involved in the synthesis of S-nitrosothiols (-SNOs). NO reacts with human hemoglobin (Hb) to produce the derivatives: S-nitrosylhemoglobin (-SNOHb) and nitrosylhemoglobin (HbNO). At neutral pH values, free NO does not react directly with the -SH groups of Hb. The reductive nitrosylation of Fe(III) heme upon reaction with NO has long been studied, but it is not yet completely known. To quantify the reaction of NO with Hb, we developed a new, sensitive (nanomolar concentration range) electrochemical assay to selectively measure HbNO and -SNOHb. The assay also allows the monitoring of free NO during the reaction with human Fe(III)Hb and Fe(II)HbO(2).

  12. Electrochemical study and analytical applications for new biologically active 2-nitrophenylbenzimidazole derivatives.

    PubMed

    Alvarez-Lueje, A; Zapata-Urzúa, C; Brain-Isasi, S; Pérez-Ortiz, M; Barros, L; Pessoa-Mahana, H; Kogan, M J

    2009-08-15

    The present study addresses the electrochemical behavior and the analytical applications of six 2-nitrophenylbenzimidazole derivatives with activity against Trypanosoma cruzi. When studied in a wide range of pH, by differential pulse polarography, tast polarography and cyclic voltammetry, these compounds exhibited two irreversible cathodic responses. With analytical purposes, the differential pulse polarography mode was selected, which exhibited adequate analytical parameters of repeatability, reproducibility and selectivity. The percentage of recovery was in all cases over 99%, and the detection and quantitation limits were at the level of 1 x 10(-7)mol L(-1) and 1 x 10(-6)mol L(-1), respectively. In addition, the differential pulse polarography method was successfully applied to study the hydrolytic degradation kinetic of one of the tested compounds. Activation energy, kinetic rate constants at different temperatures and half-life values of such application are reported.

  13. Surface treatment influences electrochemical stability of cpTi exposed to mouthwashes.

    PubMed

    Beline, Thamara; Garcia, Camila S; Ogawa, Erika S; Marques, Isabella S V; Matos, Adaias O; Sukotjo, Cortino; Mathew, Mathew T; Mesquita, Marcelo F; Consani, Rafael X; Barão, Valentim A R

    2016-02-01

    The role of surface treatment on the electrochemical behavior of commercially pure titanium (cpTi) exposed to mouthwashes was tested. Seventy-five disks were divided into 15 groups according to surface treatment (machined, sand blasted with Al2O3, and acid etched) and electrolyte solution (artificial saliva — control, 0.12% chlorhexidine digluconate, 0.05% cetylpyridinium chloride, 0.2% sodium fluoride, and 1.5% hydrogen peroxide) (n = 5). Open-circuit-potential and electrochemical impedance spectroscopy were conducted at baseline and after 7 and 14 days of immersion in each solution. Potentiodynamic test and total weight loss of disks were performed after 14 days of immersion. Scanning electron microscopy, energy dispersive spectroscopy, white light interferometry and profilometry were conducted for surface characterization before and after the electrochemical tests. Sandblasting promoted the lowest polarization resistance (Rp) (P b .0001) and the highest capacitance (CPE) (P b .006), corrosion current density (Icorr) and corrosion rate (P b .0001). In contrast, acid etching increased Rp and reduced CPE, independent to the mouthwash; while hydrogen peroxide reduced Rp (P b .008) and increased Icorr and corrosion rate (P b .0001). The highest CPE values were found for hydrogen peroxide and 0.2% sodium fluoride. Immersion for longer period improved the electrochemical stability of cpTi (P b .05). In conclusion, acid etching enhanced the electrochemical stability of cpTi. Hydrogen peroxide and sodium fluoride reduced the resistance to corrosion of cpTi, independent to the surface treatment. Chlorhexidine gluconate and cetylpyridinium chloride did not alter the corrosive behavior of cpTi.

  14. Highly specific and sensitive electrochemical genotyping via gap ligation reaction and surface hybridization detection.

    PubMed

    Huang, Yong; Zhang, Yan-Li; Xu, Xiangmin; Jiang, Jian-Hui; Shen, Guo-Li; Yu, Ru-Qin

    2009-02-25

    This paper developed a novel electrochemical genotyping strategy based on gap ligation reaction with surface hybridization detection. This strategy utilized homogeneous enzymatic reactions to generate molecular beacon-structured allele-specific products that could be cooperatively annealed to capture probes stably immobilized on the surface via disulfide anchors, thus allowing ultrasensitive surface hybridization detection of the allele-specific products through redox tags in close proximity to the electrode. Such a unique biphasic architecture provided a universal methodology for incorporating enzymatic discrimination reactions in electrochemical genotyping with desirable reproducibility, high efficiency and no interferences from interficial steric hindrance. The developed technique was demonstrated to show intrinsic high sensitivity for direct genomic analysis, and excellent specificity with discriminativity of single nucleotide variations.

  15. Imaging of a thin oxide film formation from the combination of surface reflectivity and electrochemical methods.

    PubMed

    Chakri, Sara; Patel, Anisha N; Frateur, Isabelle; Kanoufi, Frédéric; Sutter, Eliane Marie Madeleine; Tran, T T Mai; Tribollet, Bernard; Vivier, Vincent

    2017-04-13

    Electrochemical methods (cyclic voltammetry (CV), potential steps, and electrochemical impedance spectroscopy), were successfully combined with in situ reflectometry measurements for a detailed analysis of the passive layer evolution as a function of the electrode potential. Interestingly, both EIS and surface reflectivity allowed a film thickness in the nanometer range to be readily determined. In addition, transient analyses of the reflectivity simultaneously recorded with CVs show the formation of both Fe2O3 and Fe3O4 oxides. The image analysis showed that the steel surface reactivity is heterogeneous and presents micrometric islands coated with thicker oxide layer than the surrounding surface. The in situ combination of these techniques thus offers a powerful analytical description of the interface on local scale and its transient response to a perturbation.

  16. Electrospun-Technology-Derived High-Performance Electrochemical Energy Storage Devices.

    PubMed

    Xu, Mengjiao; Wang, Minxuan; Xu, Hao; Xue, Huaiguo; Pang, Huan

    2016-11-07

    Electrospinning, as a novel nontextile filament technology, is an important method to prepare continuous nanofibers and has shown its remarkable advantages, such as a broadly applicable material system, controllable fiber size and structure, and simple process. Electrospun nanofiber membranes prepared by electrospinning have shown promising applications in many fields, such as supercapacitors, lithium-ion batteries, and sodium-ion batteries, owing to their large specific surface area and adjustable network pore structure. The principle of electrospinning and key points relevant to its usage in the preparation of high-performance electrochemical energy storage materials are reviewed herein based on recent publications, particularly focusing on research progress of relative materials. Also, this review describes a distinctive conclusion and perspective on the future challenges and opportunities in electrospun nanomaterials.

  17. Synthesis of surface roughed Pt nanowires and their application as electrochemical sensors for hydrogen peroxide detection.

    PubMed

    Gao, Fan; Li, Zhiyang; Ruan, Dajiang; Gu, Zhiyong

    2014-09-01

    In this paper, platinum nanowires with roughed surface textures were fabricated by a galvanostatic electrodeposition method for electrochemical sensors toward hydrogen peroxide detection. The electrochemical behavior of the glassy carbon electrode modified with these nanowires has been studied for oxidation of hydrogen peroxide by using cyclic voltammetry and amperometry in phosphate buffer solution. Surface roughness was found to enhance the sensitivity of the Pt nanowire based electrochemical sensor towards H2O2. The Pt nanowires with rough surfaces displayed higher electrocatalytic response compared to nanowires with smooth surfaces, with a sensitivity of 171 μA mM(-1) cm(-2), and linear dynamic range up to 35 mM. The nanowire concentration effect on the sensing behavior was investigated with the best sensitivity output found at a nanowire concentration of roughly 8.6 x 10(7) number of nanowires/cm2. The new sensor also showed good anti-interference property and exhibited high accuracy when a real water sample containing H2O2 was measured.

  18. Analytical solutions for extended surface electrochemical fin models

    NASA Astrophysics Data System (ADS)

    Cassenti, Brice N.; Nelson, George J.; DeGostin, Matthew B.; Peracchio, Aldo A.; Chiu, Wilson K. S.

    2014-11-01

    Exact solutions were obtained for variations in the potential and the current for three axisymmetric geometries, with positive, negative and zero curvatures, which simulate current transport in fuel cell electrodes. These solutions can be used to assess the influence of geometry on performance for three dimensional electrode microstructures. A solid oxide fuel cell (SOFC) electrode was selected as a test case for these studies. From the exact solutions, simulations of current flow and potential drop for one dimensional networks in SOFC electrodes were performed. Numerical tests demonstrated that surfaces with positive curvature have greater current flow for the same potential drop due to higher current losses through the lateral surface area. The study also showed that zero curvature solutions will be sufficiently accurate for positive or negative curvature geometries for moderate radius changes, but differ significantly from positive or negative curvature solutions for more extreme radius changes. Analytical solutions indicate fundamental differences in geometry and its influence on current flow. Based on the results of the simulations, an approximate solution, based on one non-dimensional parameter, was developed for estimating the effects of extreme changes in cross-section area.

  19. Ethylenediamine-modified oriented MCM-41 at the electrode surface, cobalt adsorption ability and electrochemical performance.

    PubMed

    Rafiee, Mohammad; Karimi, Babak; Arshi, Simin; Vali, Hojatollah

    2014-03-28

    Mesoporous silica thin films (MCM-41) functionalized with ethylenediamine groups were electrochemically fabricated on electrode surfaces. These ligand functionalized film were a promising matrix for the immobilization of cobalt ions and preparation of cobalt complexes covalently bound to the MCM-41 support. The constructed MCM-41 were characterized by TEM, EDS and TGA analysis. This method yields uniform thin films with hexagonal mesochannels aligned and accessible to electrode surface. Well-defined electrode responses were, therefore, observed for the anchored complexes which made the electrochemical analysis of the structure possible as well. Voltammetric studies revealed the reactivity of the covalently bound complexes differed significantly from the dissolved ones. The anchored complexes preferred to be in their oxidized form which inhibits formation of oxygen adducts. The covalently bound complexes had relatively good leaching stability with good catalytic performance towards hydrogen peroxide reduction.

  20. Dynamic Characterization of Dendrite Deposition and Growth in Li-Surface by Electrochemical Impedance Spectroscopy

    SciTech Connect

    Hernandez-Maya, R; Rosas, O; Saunders, J; Castaneda, H

    2015-01-13

    The evolution of dendrite formation is characterized by DC and AC electrochemical techniques. Interfacial mechanisms for lithium deposition are described and quantified by electrochemical impedance spectroscopy (EIS) between a lithium electrode and a graphite electrode. The initiation and growth of dendrites in the lithium surface due to the cathodic polarization conditions following anodic dissolution emulate long term cycling process occurring in the lithium electrodes. The dendrite initiation at the lithium/organic electrolyte interface is proposed to be performed through a combination of layering and interfacial reactions during different cathodic conditions. The growth is proposed to be performed by surface geometrical deposition. In this work, we use EIS in galvanostatic mode to assess the initiation and growth stages of dendrites by the accumulation of precipitates formed under different current conditions. The lithium/organic solvent experimental system using frequency domain techniques is validated by the theoretical approach using a deterministic model that accounts for the faradaic processes at the interface assuming a coverage fraction of the electrodic surface affected by the dendritic growth. (C) 2015 The Electrochemical Society. All rights reserved.

  1. Electrochemical machining process for forming surface roughness elements on a gas turbine shroud

    DOEpatents

    Lee, Ching-Pang; Johnson, Robert Alan; Wei, Bin; Wang, Hsin-Pang

    2002-01-01

    The back side recessed cooling surface of a shroud defining in part the hot gas path of a turbine is electrochemically machined to provide surface roughness elements and spaces therebetween to increase the heat transfer coefficient. To accomplish this, an electrode with insulating dielectric portions and non-insulating portions is disposed in opposition to the cooling surface. By passing an electrolyte between the cooling surface and electrode and applying an electrical current between the electrode and a shroud, roughness elements and spaces therebetween are formed in the cooling surface in opposition to the insulating and non-insulating portions of the electrode, hence increasing the surface area and heat transfer coefficient of the shroud.

  2. Tip-induced nanostructuring of alloy surfaces with an electrochemical scanning tunneling microscope

    NASA Astrophysics Data System (ADS)

    Maupai, S.; Dakkouri, A. S.; Schmuki, P.

    2005-12-01

    Tip-induced nanostructuring with an electrochemical scanning tunneling microscope (EC-STM) was applied to alloy surfaces in order to resolve the reasons for the unusual stability of tip-induced metal clusters to anodic oxidation. Therefore Au thin films on glass and AuCu-alloy single crystals of different composition and surface orientation were used as substrates. The experiments give evidence that the three main factors for cluster formation and stability are the attractive interaction between tip and substrate, alloy formation during the cluster formation process as well as additional stabilization by adsorption of an underpotential deposition layer. Experimental results on the three aspects are presented and discussed.

  3. Surface and sorption properties of TIO2 nanotubes, synthesized by electrochemical anodization

    NASA Astrophysics Data System (ADS)

    Serikov, T. M.; Ibrayev, N. Kh; Smagulov, Zh

    2016-02-01

    Electrochemical anodizing of titanium metal in the fluorine-containing electrolyte was used for production of nanotubes of titanium dioxide. The surface morphology of the films was investigated by scanning electron microscopy. It was found that with increasing anodizing voltage the inner diameter, growth rate and nanotubes interporous distance is increasing. The distribution of pore volume studied by the method of adsorption and desorption of nitrogen. The specific surface area of titanium dioxide films was measured for determine the conditions of anodizing on their changes. The sorption capacity of the films was studied.

  4. Surface plasmon resonance aided electrochemical immunosensor for CK-MB determination in undiluted serum samples

    PubMed Central

    Garay, Fernando; Kisiel, Greggory; Fang, Aiping; Lindner, Ernő

    2010-01-01

    This article presents a simple chronoamperometric immunosensor for the quantitative assessment of creatine kinase MB (CK-MB) in 50 µL undiluted serum samples. The immunosensor consists of gold working and counter electrodes patterned onto a glass chip by thin-film photolithography and an external Ag|AgCl reference electrode. The detection limit (DL) of the chronoamperometric method is 13 ng mL−1 (DL = 2×RMSD/S, where RMSD is the residual mean standard deviation of the measured points around a calibration curve with a slope of S). In spiked serum samples, the response was linear up to 300 ng mL−1 of CK-MB. A surface plasmon resonance (SPR) system with simultaneous electrochemical detection (EC-SPR) aided the development of the sandwich immunoassay. Real-time monitoring of the SPR signal was used to optimize the capture antibody immobilization, CK-MB and detection antibody binding, as well as to minimize the nonspecific adsorption of serum proteins to the sensor surface. The detection antibody has been labeled with alkaline phosphatase (ALP) enzyme for sensitive electrochemical detection. ALP catalyzes the hydrolysis of ascorbic acid phosphate and generates ascorbic acid, which is measured chronoamperometrically. The electrochemical immunoassay for CK-MB was less sensitive to nonspecific adsorption related interferences, had a better detection limit, and required a lower volume of sample than the SPR method. PMID:20449577

  5. Optimization of Electrochemical Treatment Process Conditions for Distillery Effluent Using Response Surface Methodology.

    PubMed

    Arulmathi, P; Elangovan, G; Begum, A Farjana

    2015-01-01

    Distillery industry is recognized as one of the most polluting industries in India with a large amount of annual effluent production. In this present study, the optimization of electrochemical treatment process variables was reported to treat the color and COD of distillery spent wash using Ti/Pt as an anode in a batch mode. Process variables such as pH, current density, electrolysis time, and electrolyte dose were selected as operation variables and chemical oxygen demand (COD) and color removal efficiency were considered as response variable for optimization using response surface methodology. Indirect electrochemical-oxidation process variables were optimized using Box-Behnken response surface design (BBD). The results showed that electrochemical treatment process effectively removed the COD (89.5%) and color (95.1%) of the distillery industry spent wash under the optimum conditions: pH of 4.12, current density of 25.02 mA/cm(2), electrolysis time of 103.27 min, and electrolyte (NaCl) concentration of 1.67 g/L, respectively.

  6. Room-temperature Electrochemical Synthesis of Carbide-derived Carbons and Related Materials

    SciTech Connect

    Gogotsi, Yury

    2015-02-28

    This project addresses room-temperature electrochemical etching as an energy-efficient route to synthesis of 3D nanoporous carbon networks and layered 2D carbons and related structures, as well as provides fundamental understanding of structure and properties of materials produced by this method. Carbide-derived-carbons (CDCs) are a growing class of nanostructured carbon materials with properties that are desirable for many applications, such as electrical energy and gas storage. The structure of these functional materials is tunable by the choice of the starting carbide precursor, synthesis method, and process parameters. Moving from high-temperature synthesis of CDCs through vacuum decomposition above 1400°C and chlorination above 400°C, our studies under the previous DOE BES support led to identification of precursor materials and processing conditions for CDC synthesis at temperatures as low as 200°C, resulting in amorphous and highly reactive porous carbons. We also investigated synthesis of monolithic CDC films from carbide films at 250-1200°C. The results of our early studies provided new insights into CDC formation, led to development of materials for capacitive energy storage, and enabled fundamental understanding of the electrolyte ions confinement in nanoporous carbons.

  7. Correlation of Spectral and Electrochemical Properties of a Series of Ferrocene Derivatives

    NASA Technical Reports Server (NTRS)

    Hepp, Aloysius F.; Wrighton, Mark S.

    2016-01-01

    Charge-transfer-to-solvent (CTTS) bands are observed in the UV/VIS spectra of a series of ferrocene derivatives (ferrocene; 1,1'-dimethyl; 1,2,3,4,5-pentamethyl; 1,2,3,4,l',2',3',4'-octamethyl; and decamethyl) by the addition of increasing amounts of CCl4 to ethanol solutions. A linear correlation (slope = 8540 cm-1/V) was found between the redox potential and the energy of the CTTS band, consistent with electrochemical and photochemical oxidation by removal of an electron from the same molecular orbital. Inclusion of literature data for ruthenocene and [(?5-C5H5)Fe(CO)]4 results in a line with a slope of 8140 cm-1/V, within 1 percent of the wavenumber to electron volt conversion factor. Calculation of association constants (K) shows a slight decrease (1.2 to 0.7 mole fraction-1) as the bulkiness of the cyclopentadienyl ring increases, consistent with either a steric or a repulsive electronic effect. The extinction coefficient of the CTTS absorption was constant at approximately 1700/M/cm.

  8. Facile Electrochemical Method to Improve Surface Features of Pure Copper in Dilute Basic Solutions

    NASA Astrophysics Data System (ADS)

    Fattah-alhosseini, Arash; Imantalab, Omid; Attarzadeh, Farid Reza; Attarzadeh, Navid

    2017-03-01

    Electrochemical properties of coarse and nano-grained pure copper can be modified and improved effectively through applying cyclic potentiodynamic passivation (CPP) treatment. It is found that the success of this method depends up to a large extent on grain size. Eight passes of accumulative roll bonding processing are successfully used at room temperature to produce nano-grained pure copper. Transmission electron microscopy image and selected area diffraction pattern both attest to the occurrence of intense grain refinement under the influence of aforementioned process, in which an average grain size <100 nm is attainable. Using several electrochemical characterization methods reveals that CPP treatment fully exploits potentials of nano-grained samples to form a dense and thick protective passive film. It is speculated that high-quality passive layers relate to the presence of high-density structural defects on the surface of nano-grained samples.

  9. Infrared characterization and electrochemical study of γ-methacryloxypropyltrimethoxysilane grafted in to surface of copper.

    PubMed

    Masmoudi, M; Abdelmouleh, M; Abdelhedi, R

    2014-01-24

    The formation of a protective layer of γ-methacryloxypropyltrimethoxysilane (γ-MPS) on copper is studied by diffuse reflectance infrared spectroscopy (DRIFT), gravimetric chemical (weight loss) and electrochemical (cyclic voltammetry and potentiodynamic polarization) measurements. By simple immersion in the silanic bath (90/5/5 v/v ethanol/water/silane), this agent immediately physisorbed on copper, but the protective effects are poor. Thiolate and siloxane band formation improve the performances of the silanic layer on the surface of copper especially after heat treatment process. Chemical and electrochemical measurements show that the protective action of heat treatment (HT/Cu-MPS) process is higher than that of aged process (aged/Cu-MPS).

  10. Spectrophotochemical and electrochemical characterization of perylene derivatives adsorbed on nanoporous metaloxide films

    NASA Astrophysics Data System (ADS)

    Kus, M.; Demic, S.; Zafer, C.; Saygili, G.; Bilgili, H.; Icli, S.

    2007-03-01

    Electrochemistry of perylene imide and anhydride derivatives adsorbed on semiconductor TiO{2} (NT) and insulator Al{2}O{3} (NA) metal oxide films were presented. Adsorption rates on metal oxide surface are observed to be strongly depending on molecular structure. Monoanhydride-monoimide derivatives show two reversible reductions in solution and one reversible reduction in films. Color change from red to blue and violet is observed indicating the formation of monoanion and dianion radicals. Spectroelectrochemical measurements support this interpretation. The color reversal is quite stable in NA films in comparison with NT films. This paper has been presented at “ECHOS06”, Paris, 28 30 juin 2006.

  11. Electrochemical decolorization of dye wastewater by surface-activated boron-doped nanocrystalline diamond electrode.

    PubMed

    Chen, Chienhung; Nurhayati, Ervin; Juang, Yaju; Huang, Chihpin

    2016-07-01

    Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes (EAOPs) to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process. The performance of boron-doped nanocrystalline diamond (BD-NCD) film electrode for decolorization of Acid Yellow (AY-36) azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic. Due to the oxidation of surface functional groups and some portion of sp(2) carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation (EO) capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand (COD) removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species.

  12. Surface functionalization of fluorine-doped tin oxide samples through electrochemical grafting.

    PubMed

    Lamberti, F; Agnoli, S; Brigo, L; Granozzi, G; Giomo, M; Elvassore, N

    2013-12-26

    Transparent conductive oxides are emerging materials in several fields, such as photovoltaics, photoelectrochemistry, and optical biosensing. Their high chemical inertia, which ensured long-term stability on one side, makes challenging the surface modification of transparent conductive oxides; long-term robust modification, high yields, and selective surface modifications are essential prerequisite for any further developments. In this work, we aim at inducing chemical functionality on fluorine-doped tin oxide surfaces (one of the most inexpensive transparent conductive oxide) by means of electrochemical grafting of aryl diazonium cations. The grafted layers are fully characterized by photoemission spectroscopy, cyclic voltammetry, and atomic force microscopy showing linear correlation between surface coverage and degree of modification. The electrochemical barrier effect of modified surfaces was studied at different pH to characterize the chemical nature of the coating. We showed immuno recognition of biotin complex built onto grafted fluorine-doped tin oxides, which opens the perspective of integrating FTO samples with biological-based devices.

  13. Surface Layer Evolution on Graphite During Electrochemical Sodium-tetraglyme Co-intercalation.

    PubMed

    Maibach, Julia; Jeschull, Fabian; Brandell, Daniel; Edström, Kristina; Valvo, Mario

    2017-04-12

    One obstacle in sodium ion batteries is the lack of suitable anode materials. As recently shown, the most common anode material of the state of the art lithium ion batteries, graphite, can be used for sodium ion storage as well, if ether-based electrolyte solvents are used. These solvents cointercalate with the sodium ions leading to the highly reversible formation of ternary graphite intercalation compounds (t-GIC). In order for the solvent cointercalation to work efficiently, it is expected that only a very thin surface layer forms during electrochemical cycling. In this article, we therefore present the first dedicated study of the surface layer evolution on t-GICs using soft X-ray photoelectron spectroscopy. This technique with its inherent high surface sensitivity and low probing depth is an ideal tool to study the underlying interfacial reactions during the sodiation and desodiation of graphite. In this report, we apply this approach to graphite composite electrodes cycled in Na half cells with a 1 M sodium bis(fluorosulfonyl)imide/tetraethylene glycol dimethyl ether (NaFSI/TEG-DME) electrolyte. We have found a surface layer on the cycled electrodes, mainly composed of salt decomposition products and hydrocarbons, in line with irreversible capacity losses observed in the electrochemical cycling. Although this surface layer does not seem to block cointercalation completely, it seems to affect its efficiency resulting in a low Coulombic efficiency of the studied battery system.

  14. Electrochemical performance of carbide-derived carbon anodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Yeon, Sun-Hwa; Jung, Kyu-Nam; Yoon, Sukeun; Shin, Kyoung-Hee; Jin, Chang-Soo

    2013-07-01

    Carbide-derived carbons (CDCs), part of a large family of carbon materials derived from carbide, are attractive for energy-related applications, such as batteries, supercapacitors, and fuel cells. Pore textures (micro-, meso-, and macro-pores) and structures (from amorphous to highly ordered graphite) of CDCs can be controlled by changing the synthesis conditions and carbide precursor. Adequate control of the carbon structure, and the porosity in terms of application as an anode can be exploited to maximize the electrochemical capacity in a lithium ion batteries. In this study, the use of CDC as anodes by chlorine treatment of B4C and TiC7N3 in a synthesis temperature range from 600 °C to 1200 °C has been explored. The discharge capacity of TiC7N3-CDC reaches the highest value, 462 mA h g-1, at 100 cycles, which is 25% higher than the theoretical capacity of graphite (375 mA h g-1). B4C-CDC meanwhile affords a value of 453 mA h g-1 at 100 cycles. These results show that B4C-CDC and TiC7N3-CDC have excellent potential as the negative electrode in Li battery applications, and can be exposed to a practical low synthesis temperature range of 600-1200 °C. B4C-CDC and TiC7N3-CDC can also provide 2-3 times better performance than existing graphite or hard carbon for lithium battery systems.

  15. Electrochemical Imaging and Redox Interrogation of Surface Defects on Operating SrTiO3 Photoelectrodes.

    PubMed

    Simpson, Burton H; Rodríguez-López, Joaquín

    2015-12-02

    We introduce electrochemical imaging and nano-resolved measurements of catalytic intermediates on operating SrTiO3 photoelectrodes. Spatially resolved redox titrations of photogenerated reactive oxygen species (ROS) were used to profile changes in ROS coverage and reactivity at pristine and ion-milled defective areas on n-doped (100) SrTiO3. Adsorbed ROS reached a potential-dependent limiting coverage of ∼0.1 monolayer and did not differ significantly between milled and pristine areas. However, the reaction kinetics between a solution-phase mediator and adsorbed ROS were found to be significantly decreased over ion-milled areas. Using a nanoelectrode, we resolved ksi values of 5 and 300 m(3)/s·mol for these bimolecular reactions at defective and pristine sites, respectively. Ion-milled areas also showed significantly decreased activity toward photo-oxidations, providing evidence that photogenerated ROS mediate fast charge-transfer reactions with solution-phase species at the semiconductor-electrolyte interface. Our results provide spatially resolved direct evidence of the impact of surface defects on the performance of photoelectrochemical systems. Scanning electrochemical microscopy offers a powerful method for evaluating the reactivity of an operating electrochemical interface by using redox titrations that detected as few as 30 attomoles of adsorbed ROS.

  16. Effects of CO{sub 2} activation on electrochemical performance of microporous carbons derived from poly(vinylidene fluoride)

    SciTech Connect

    Lee, Seul-Yi; Park, Soo-Jin

    2013-11-15

    In this work, we have prepared microporous carbons (MPCs) derived from poly(vinylidene fluoride) (PVDF), and the physical activation of MPCs using CO{sub 2} gas is subsequently carried out with various activation temperatures to investigate the electrochemical performance. PVDF is successfully converted into MPCs with a high specific surface area and well-developed micropores. After CO{sub 2} activation, the specific surface areas of MPCs (CA-MPCs) are enhanced by 12% compared with non-activated MPCs. With increasing activation temperature, the micropore size distributions of A-MPCs also become narrower and shift to larger pore size. It is also confirmed that the CO{sub 2} activation had developed the micropores and introduced the oxygen-containing groups to MPCs′ surfaces. From the results, the specific capacitances of the electrodes in electric double layer capacitors (EDLCs) based on CA-MPCs are distinctly improved through CO{sub 2} activation. The highest specific capacitance of the A-MPCs activated at 700 °C is about 125 F/g, an enhancement of 74% in comparison with NA-MPCs, at a discharge current of 2 A/g in a 6 M KOH electrolyte solution. We also found that micropore size of 0.67 nm has a specific impact on the capacitance behaviors, besides the specific surface area of the electrode samples. - Graphical abstract: The A-MPC samples with high specific surface area (ranging from 1030 to 1082 m{sup 2}/g), corresponding to micropore sizes of 0.67 and 0.72 nm, and with the amount of oxygen-containing groups ranging from 3.2% to 4.4% have been evaluated as electrodes for EDLC applications. . Display Omitted - Highlights: • Microporous carbons (MPCs) were synthesized without activation process. • Next, we carried out the CO{sub 2} activation of MPCs with activation temperatures. • It had developed the micropores and introduced the O-functional groups to MPCs. • The highest specific capacitance: 125 F/g, an increase of 74% compared to MPCs.

  17. Electrochemical Oxidative Decarboxylation of Malonic Acid Derivatives: A Method for the Synthesis of Ketals and Ketones.

    PubMed

    Ma, Xiaofeng; Luo, Xiya; Dochain, Simon; Mathot, Charlotte; Markò, István E

    2015-10-02

    A novel electrochemical oxidative decarboxylation of disubstituted malonic acids leading to dimethoxy ketals is described. In the presence of NH3, a wide range of disubstituted malonic acids was transformed into the corresponding ketals in good to excellent yields under electrochemical conditions. When the crude reaction mixture, obtained after electrolysis, was directly treated with 1 M aq HCl, the initially generated ketals were smoothly transformed into the corresponding ketones in a single vessel operation.

  18. Performance of an electrochemical COD (chemical oxygen demand) sensor with an electrode-surface grinding unit.

    PubMed

    Geun Jeong, Bong; Min Yoon, Seok; Ho Choi, Chang; Koang Kwon, Kil; Sik Hyun, Moon; Heui Yi, Dong; Soo Park, Hyung; Kim, Mia; Joo Kim, Hyung

    2007-12-01

    An electrochemical COD (chemical oxygen demand) sensor using an electrode-surface grinding unit was investigated. The electrolyzing (oxidizing) action of copper on an organic species was used as the basis of the COD measuring sensor. Using a simple three-electrode cell and a surface grinding unit, the organic species is activated by the catalytic action of copper and oxidized at a working electrode, poised at a positive potential. When synthetic wastewater was fed into the system, the measured Coulombic yields were found to be dependent on the COD of the synthetic wastewater. A linear correlation between the Coulombic yields and the COD of the synthetic wastewater was established (10-1000 mg L(-1)) when the electrode-surface grinding procedure was activated briefly at 8 h intervals. When various kinds of wastewater samples obtained from various sewage treatment plants were measured, linear correlations (r(2)> or = 0.92) between the measured EOD (electrochemical oxygen demand) value and COD of the samples were observed. At a practical wastewater treatment plant, the measurement system was successfully operated with high accuracy and good stability over 3 months. These experimental results show that the application of the measurement system would be a rapid and practical method for the determination of COD in water industries.

  19. Electrochemical formation and characterization of Au nanostructures on a highly ordered pyrolytic graphite surface

    NASA Astrophysics Data System (ADS)

    Gómez, José J. Arroyo; Zubieta, Carolina; Ferullo, Ricardo M.; García, Silvana G.

    2016-02-01

    The electrochemical formation of Au nanoparticles on a highly ordered pyrolytic graphite (HOPG) substrate using conventional electrochemical techniques and ex-situ AFM is reported. From the potentiostatic current transients studies, the Au electrodeposition process on HOPG surfaces was described, within the potential range considered, by a model involving instantaneous nucleation and diffusion controlled 3D growth, which was corroborated by the microscopic analysis. Initially, three-dimensional (3D) hemispherical nanoparticles distributed on surface defects (step edges) of the substrate were observed, with increasing particle size at more negative potentials. The double potential pulse technique allowed the formation of rounded deposits at low deposition potentials, which tend to form lines of nuclei aligned in defined directions leading to 3D ordered structures. By choosing suitable nucleation and growth pulses, one-dimensional (1D) deposits were possible, preferentially located on step edges of the HOPG substrate. Quantum-mechanical calculations confirmed the tendency of Au atoms to join selectively on surface defects, such as the HOPG step edges, at the early stages of Au electrodeposition.

  20. Electrochemical analysis of the UV treated bactericidal Ti6Al4V surfaces.

    PubMed

    Pacha-Olivenza, Miguel A; Gallardo-Moreno, Amparo M; Vadillo-Rodríguez, Virginia; González-Martín, M Luisa; Pérez-Giraldo, Ciro; Galván, Juan C

    2013-04-01

    This research investigates in detail the bactericidal effect exhibited by the surface of the biomaterial Ti6Al4V after being subjected to UV-C light. It has been recently hypothesized that small surface currents, occurring as a consequence of the electron-hole pair recombination taking place after the excitation process, are behind the bactericidal properties displayed by this UV-treated material. To corroborate this hypothesis we have used different electrochemical techniques, such as electrochemical impedance spectroscopy (EIS), potentiodynamic polarization plots and Mott-Schottky plots. EIS and Mott-Schottky plots have shown that UV-C treatment causes an initial increase on the surface electrical conduction of this material. In addition, EIS and polarization plots demonstrated that higher corrosion currents occur at the UV treated than at the non-irradiated samples. Despite this increase in the corrosion currents, EIS has also shown that such currents are not likely to affect the good stability of this material oxide film since the irradiated samples completely recovered the control values after being stored in dark conditions for a period not longer than 24h. These results agree with the already-published in vitro transitory behavior of the bactericidal effect, which was shown to be present at initial times after the biomaterial implantation, a crucial moment to avoid a large number of biomaterial associated infections.

  1. Potential-dependent adsorption/desorption behavior of perfluorosulfonated ionomer on a gold electrode surface studied by cyclic voltammetry, electrochemical quartz microbalance, and electrochemical atomic force microscopy.

    PubMed

    Masuda, Takuya; Ikeda, Kota; Uosaki, Kohei

    2013-02-19

    Potential-dependent adsorption/desorption behavior of perfluorosulfonated ionomer (PFSI) on a gold electrode was investigated by cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), and electrochemical atomic force microscopy (EC-AFM) in a Nafion (i.e., PFSI) dispersed aqueous solution without any other electrolyte. It was found that PFSI serves as an electrolyte and that electrochemical measurements can be performed in this solution without any significant IR drop. PFSI molecules were adsorbed on the Au surface in the lying-down configuration in the potential range between 0 and 0.45 V, the amount of adsorbed PFSI increased when the potential was made more positive than 0.75 V, and the adsorbed PFSI fully desorbed from the surface at potentials more positive than 1.4 V where gold oxide was formed. Once the gold oxide had been reduced, PFSI readsorbed on the surface, albeit slowly. PFSI desorbed from the surface as the potential was made more negative than 0 V. These processes took place reversibly.

  2. Electrochemically Created Highly Surface Roughened Ag Nanoplate Arrays for SERS Biosensing Applications

    PubMed Central

    Slotcavage, Daniel; Mai, John D.; Guo, Feng; Li, Sixing; Zhao, Yanhui; Lei, Yong; Cameron, Craig E.

    2014-01-01

    Highly surface-roughened Ag nanoplate arrays are fabricated using a simple electrodeposition and in situ electrocorrosion method with inorganic borate ions as capping agent. The electrocorrosion process is induced by a change in the local pH value during the electrochemical growth, which is used to intentionally carve the electrodeposited structures. The three dimensionally arranged Ag nanoplates are integrated with substantial surface-enhanced Raman scattering (SERS) hot spots and are free of organic contaminations widely used as shaping agents in previous works, making them excellent candidate substrates for SERS biosensing applications. The SERS enhancement factor of the rough Ag nanoplates is estimated to be > 109. These Ag nanoplate arrays are used for SERS-based analysis of DNA hybridization monitoring, protein detection, and virus differentiation without any additional surface modifications or labelling. They all exhibit an extremely high detection sensitivity, reliability, and reproducibility. PMID:25383191

  3. Domain Derivatives in Dielectric Rough Surface Scattering

    DTIC Science & Technology

    2015-01-01

    written as the directional derivative: φ̇(~x) = d dτ (φ · Tτ )|τ=0 = d dτ φτ (τ, ~xτ )|τ=0. (9) φ̇, as defined in (8) (or (9)), is a Gateaux differential...Ωτ φτ (~xτ ) d ~xτ be a domain functional of φτ over the perturbed domain, Ωτ . It can be written as: F (φτ ; Ω) = ∫ Ω φτ (~x+ τ ~V (~x)) |JT... d ~x. (14) 7 Approved for public release; distribution unlimited |JT | is the Jacobian matrix of Tτ , and (JT )ij = δij+Vi,j, Vi,j = ∂Vi/∂xj . Direct

  4. Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions.

    PubMed

    Mueller, David N; Machala, Michael L; Bluhm, Hendrik; Chueh, William C

    2015-01-19

    Surface redox-active centres in transition-metal oxides play a key role in determining the efficacy of electrocatalysts. The extreme sensitivity of surface redox states to temperatures, to gas pressures and to electrochemical reaction conditions renders them difficult to investigate by conventional surface-science techniques. Here we report the direct observation of surface redox processes by surface-sensitive, operando X-ray absorption spectroscopy using thin-film iron and cobalt perovskite oxides as model electrodes for elevated-temperature oxygen incorporation and evolution reactions. In contrast to the conventional view that the transition metal cations are the dominant redox-active centres, we find that the oxygen anions near the surface are a significant redox partner to molecular oxygen due to the strong hybridization between oxygen 2p and transition metal 3d electronic states. We propose that a narrow electronic state of significant oxygen 2p character near the Fermi level exchanges electrons with the oxygen adsorbates. This result highlights the importance of surface anion-redox chemistry in oxygen-deficient transition-metal oxides.

  5. In vitro bioactivity investigations of Ti-15Mo alloy after electrochemical surface modification.

    PubMed

    Kazek-Kęsik, Alicja; Kuna, Karolina; Dec, Weronika; Widziołek, Magdalena; Tylko, Grzegorz; Osyczka, Anna M; Simka, Wojciech

    2016-07-01

    Titanium and its aluminum and vanadium-free alloys have especially great potential for medical applications. Electrochemical surface modification improves their surface bioactivity and stimulates osseointegration process. In this work, the effect of plasma electrolytic oxidation of the β-type alloy Ti-15Mo surface on its bioactivity is presented. Bioactivity of the modified alloy was investigated by immersion in simulated body fluid (SBF). Biocompatibility of the modified alloys were tested using human bone marrow stromal cells (hBMSC) and wild intestinal strains (DV/A, DV/B, DV/I/1) of Desulfovibrio desulfuricans bacteria. The particles of apatite were formed on the anodized samples. Human BMSC cells adhered well on all the examined surfaces and expressed ALP, collagen, and produced mineralized matrix as determined after 10 and 21 days of culture. When the samples were inoculated with D. desulfuricans bacteria, only single bacteria were visible on selected samples. There were no obvious changes in surface morphology among samples. Colonization and bacterial biofilm formation was observed on as-ground sample. In conclusion, the surface modification improved the Ti-15Mo alloy bioactivity and biocompatibility and protected surface against colonization of the bacteria. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 903-913, 2016.

  6. Soft Surfaces for Fast Characterization and Positioning of Scanning Electrochemical Microscopy Nanoelectrode Tips.

    PubMed

    Gossage, Zachary T; Simpson, Burton H; Schorr, Noah B; Rodríguez-López, Joaquín

    2016-10-18

    The testing of nanoelectrode tips for scanning electrochemical microscopy (SECM) is a slow and cumbersome task that often results in untimely electrode breakage due to crashing against a substrate. Here, we evaluated approach curves of nano- and microelectrodes to soft surfaces using SECM for a rapid and more convenient characterization and positioning protocol. Soft surfaces consisted of either a submerged argon bubble or a thin polydimethylsiloxane (PDMS) layer. While approach curves to Ar bubbles in the presence of a surfactant were promising for the characterization of microelectrode tips, their performance with nanoelectrodes was deficient. In contrast, approach curves to PDMS films allowed the rapid positioning of nanoelectrodes as small as 30 nm radius at speeds up to 5 μm/s without the risk of breakage. The nanoelectrodes were able to approach the polymer films multiple times without affecting their electrochemical performance. Furthermore, using a half-coated substrate with PDMS, nanoelectrodes could be retracted and positioned very close to the bare, hard substrate for characterization with traditional approach curves. We estimate time savings on tip characterization/positioning on the order of 10- to 100-fold. This simple procedure is easily implemented without the requirement of additional devices supplementing existing commercial SECM instruments.

  7. Superhydrophobic surface-based magnetic electrochemical immunoassay for detection of Schistosoma japonicum antibodies.

    PubMed

    Nie, Jinfang; Zhang, Yun; Wang, Hua; Wang, Shiping; Shen, Guoli

    2012-03-15

    In this paper, a magnetic electrochemical immunoassay that uses a superhydrophobic surface-based analytical platform (SSAP) has been initially developed for detection of Schistosoma japonicum (Sj) antibodies (SjAb). The SSAP is fabricated by modifying the inner surfaces of plastic test tubes with superhydrophobic polycarbonate coatings that show a water contact angle up to 160° and a water rolling angle less than 5°. In a noncompetitive sandwich format, the SjAb immunoassay with magnetic particles is based on sensitive stripping voltammetry analysis coupled with the copper enhanced Au nanoparticle tag amplification. This technique is quantitatively sensitive to SjAb concentrations ranging from 2 ng ml(-1) to 15 μg ml(-1), with a detection limit of ∼1.3 ngml(-1). Moreover, the results of assaying several serum specimens prove its feasibility of practical applications. The self-cleaning SSAP can be reused, because no aqueous samples reagents or contaminate the superhydrophobic polycarbonate during the experiments. The comparison study additionally demonstrates that the SSAP-based magnetic electrochemical immunoassays can offer preferable advantages over the existing approaches for SjAb detection, in terms of volumes of samples and reagents, assay time, and detection limit.

  8. Surface electrochemical control for fine coal and pyrite separation. Technical progress report, January 1, 1990--March 31, 1990

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Bodily, D.M.; Wadsworth, M.E.

    1990-12-31

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  9. Surface electrochemical control for the fine coal and pyrite separation. Technical progress report, July 21, 1989--September 30, 1989

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Wadsworth, M.E.

    1989-12-31

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  10. Surface electrochemical control for the fine coal and pyrite separation. Technical progress report, October 1, 1989--December 31, 1989

    SciTech Connect

    Chen, Wanxiong; Hu, Weibai; Wann, Jyi-Perng; Zhu, Ximeng; Wadsworth, M.E.; Bodily, D.M.

    1989-12-31

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  11. Surface electrochemical control for the fine coal and pyrite separation. Technical progress report, January 1, 1992--March 31, 1992

    SciTech Connect

    Hu, Weibai; Huang, Qinping; Zhu, Ximeng; Li, Jun; Bodily, D.M.; Liang, Jun; Zhong, Tingke; Wadsworth, M.E.

    1992-07-01

    Ongoing work includes the characterization of coal pyrites, the floatability evaluation of typical US coal samples, the flotation behavior of coal pyrites, the electrochemical measurement of the surface properties of coal pyrites, and the characterization of species produced at pyrite surfaces.

  12. Magnetic control of electrochemical processes at electrode surface using iron-rich graphene materials with dual functionality.

    PubMed

    Lim, Chee Shan; Ambrosi, Adriano; Sofer, Zdeněk; Pumera, Martin

    2014-07-07

    Metal-doped graphene hybrid materials demonstrate promising capabilities in catalysis and various sensing applications. There also exists great interest for on-demand control of the selectivity of many electrochemical processes. In this work, an iron-doped thermally reduced graphene oxide (Fe-TRGO) was prepared and used to investigate the possibility of a reproducible, magnetically controlled method to modulate electrochemical reactivities through a scalable method. We made use of the presence of both magnetic and electrocatalytic properties in the Fe-TRGOs to induce attraction and removal of the Fe-TRGO material onto and off the working electrode surfaces magnetically, thereby controlling the electrochemical oxidation and reduction processes. The outstanding electrochemical performance of the Fe-TRGO material was evident, with enhanced current signals and lower peak potentials observed upon magnetic activation. Reversible and reproducible cycles of activation and deactivation were obtained as the peak heights and peak potentials remained relatively consistent with no apparent carryover between every step. Both components of Fe-TRGO play an electrocatalytic role in the electrochemical sensing. In the cases of the oxygen reduction reaction and reduction of cumene hydroperoxide, the iron oxide plays the role of an electrocatalyst, while in the cases of ascorbic acid, the enhanced electroactivity originates from the high surface area of the graphene portion in the Fe-TRGO hybrid material. The feasibility of this magnetically switchable method for on-demand sensing and energy production thus brings about potential developments for future electrochemical applications.

  13. Magnetic control of electrochemical processes at electrode surface using iron-rich graphene materials with dual functionality

    NASA Astrophysics Data System (ADS)

    Lim, Chee Shan; Ambrosi, Adriano; Sofer, Zdeněk; Pumera, Martin

    2014-06-01

    Metal-doped graphene hybrid materials demonstrate promising capabilities in catalysis and various sensing applications. There also exists great interest for on-demand control of the selectivity of many electrochemical processes. In this work, an iron-doped thermally reduced graphene oxide (Fe-TRGO) was prepared and used to investigate the possibility of a reproducible, magnetically controlled method to modulate electrochemical reactivities through a scalable method. We made use of the presence of both magnetic and electrocatalytic properties in the Fe-TRGOs to induce attraction and removal of the Fe-TRGO material onto and off the working electrode surfaces magnetically, thereby controlling the electrochemical oxidation and reduction processes. The outstanding electrochemical performance of the Fe-TRGO material was evident, with enhanced current signals and lower peak potentials observed upon magnetic activation. Reversible and reproducible cycles of activation and deactivation were obtained as the peak heights and peak potentials remained relatively consistent with no apparent carryover between every step. Both components of Fe-TRGO play an electrocatalytic role in the electrochemical sensing. In the cases of the oxygen reduction reaction and reduction of cumene hydroperoxide, the iron oxide plays the role of an electrocatalyst, while in the cases of ascorbic acid, the enhanced electroactivity originates from the high surface area of the graphene portion in the Fe-TRGO hybrid material. The feasibility of this magnetically switchable method for on-demand sensing and energy production thus brings about potential developments for future electrochemical applications.

  14. Electrochemical insertion of lithium into polymer derived silicon oxycarbide and oxycarbonitride ceramics

    NASA Astrophysics Data System (ADS)

    Ahn, Dongjoon

    There has recently been great interest in lithium storage at the anode of Li-ion rechargeable battery in order to replace the carbon-based anode. Over the last two decades, carbon-based anode, especially graphite, was utilized as anode in lithium ion batteries because of its cyclic stability and coulombic efficiency. However, low capacity and the thermal runaway resulted from the solid electrolyte interface (SEI) formation on the graphite anode during charging and discharging cycles. This inhibited the further development of lithium ion batteries for Plug-in Hybrid Electrical Vehicle (PHEV) or Electrical Vehicle (EV) which demand both high energy and high power density. The goal of this research was to develop the anode material, Silicon Oxycarbide (SixOyCz) and Silicon Carbonitride (SixCyNz), from Polymer Derived Ceramics (PDCs) for lithium-ion batteries application and to understand the thermodynamics and kinetics of intercalation mechanism in the host material. This includes as three main categories: (1) Characterization of PDCs, (2) measurement of electrochemical phenomena of PDCs anode in half-cell which used lithium foil as anode, (3) analysis of the lithium intercalation mechanism and diffusion coefficient in PDCs. In this thesis, the first objective was to synthesize possible anode materials and construct the proper battery structure to experiment its intercalation and deintercalation behaviors. Also, various experiments such as cyclic stability, capacity retention and C-rate capability were performed in order to estimate the feasibility of PDCs as new anode materials for the next generation. The second objective was to determine the reversible and irreversible capacity from different fraction of Si, C, O and N composition. Based on this analysis, the mixed bond sites in SixOyCz had higher reversible and irreversible capacity than the free carbon sites. The third objective was to examine the hysteretic response of lithium intercalation to SiCO. According to

  15. Ellipsometric and Electrochemical Characterization of Charge Transport in Electroactive Polymers and of the Surface Phase Produced by Electrochemical Activation of Glassy Carbon Electrodes

    NASA Astrophysics Data System (ADS)

    Kepley, Larry Joe

    1990-01-01

    In situ ellipsometry was used to study the electrodeposition of polymer films formed by oxidation of bipyrazine, polyvinylferrocene (PVF), and aniline; the deposition of a viologen-containing siloxane polymer (PQ^{2+/+}) formed by electroreduction of N,N^' -bis (-3-(trimethoxysilyl)propyl) -4,4^ '-bipyridinium dichloride (I) solutions and by spin-casting solutions of I; and the oxidation-dependent swelling of spin-cast films of two structurally similar, ferrocene-containing polyamides. Electrodeposited films displayed good optical characteristics (i.e., high reflectivity, uniform coverage, and homogeneity) for thicknesses up to 400 nm in some cases. Nonideal illipsometric behavior was observed when film morphology varied with film growth. The complex refractive index, film thickness, and the viologen and ferrocene concentrations in the films were measured as a function of oxidation state, both during depositions and after transferring coated-electrodes into blank electrolyte solutions. The voltammetry of the redox polymers was studied and charge-transport modeled by finite -difference simulations of charge diffusion and diffusion coupled to dimerization/monomerization reactions. Equations were derived for linear-sweep voltammetry of a reversible couple in equilibrium with its dimer in a thin-layer cell. Ellipsometric data during electrolysis of the redox films by potential sweeps and steps were compared to theoretical curves for diffusional transport to determine the mechanism of charge transport and to optically measure its rate. The influence of redox-induced thickness changes and solvent sorption on charge transport and voltammetric behavior is described. The electrochemical activation of glassy carbon electrodes for electrolysis of aromatic molecules, such as catechol and hydroquinone, was studied by combined ellipsometric and voltammetric measurements. Ellipsometry was used to detect the anodic growth of nearly transparent layer which activated the surface. X

  16. Photochemically controlled electrochemical deposition and dissolution of Ag0 nanoclusters on au electrode surfaces.

    PubMed

    Riskin, Michael; Katz, Eugenii; Gutkin, Vitaly; Willner, Itamar

    2006-12-05

    A photoisomerizable thiolated nitrospiropyran SP, (1a), monolayer is assembled on a Au electrode by the primary deposition of thiolated nitromerocyanine isomer 1b as a monolayer on the electrode, followed by the irradiation of the surface with visible light, lambda > 475 nm. The surface coverage of nitrospiropyran units (1a) on the electrode is 2 x 10-10 mole cm-2. Irradiation of the electrode with UV light, 320 nm < lambda < 360 nm, results in the nitromerocyanine, MR, monolayer on the electrode that binds Ag+ ions to the phenolate units. The Ag+ ions associated with the MR monolayer undergo cyclic reduction to surface-confined Ag0 nanoclusters, and reoxidation and dissolution of the Ag0 nanoclusters to Ag+ ions associated with the monolayer are demonstrated. The electron-transfer rate constants for the reduction of Ag+ to Ag0 and for the dissolution of Ag0 were determined by chronoamperometry and correspond to ketred = 12.7 s-1 and ketox = 10.5 s-1, respectively. The nanoclustering rate was characterized by surface plasmon resonance measurements, and it proceeds on a time scale of 10 min. The size of the Ag0 nanoclusters is in the range of 2 to 20 nm. The electrochemically induced reduction of the MR-Ag+ monolayer to the MR-Ag0 surface and the reoxidation of the MR-Ag0 surface control the hydrophilic-hydrophobic properties of the surface. The advancing contact angle of the MR-Ag0-functionalized surface is 59 degrees , and the contact angle of the MR-Ag+-monolayer-functionalized surface is 74 degrees . Photoisomerization of the Ag0-MR surface to the Ag0-SP state, followed by the oxidation of the Ag0 nanoclusters, results in the dissolution of the Ag+ ions into the electrolyte solution.

  17. Photogeneration of singlet oxygen by the phenothiazine derivatives covalently bound to the surface-modified glassy carbon

    NASA Astrophysics Data System (ADS)

    Blacha-Grzechnik, Agata; Piwowar, Katarzyna; Krukiewicz, Katarzyna; Koscielniak, Piotr; Szuber, Jacek; Zak, Jerzy K.

    2016-05-01

    The selected group of four amine-derivatives of phenothiazine was covalently grafted to the glassy carbon surface in the four-step procedure consisting of the electrochemical reduction of the diazonium salt followed by the electrochemical and chemical post-modification steps. The proposed strategy involves the bonding of linker molecule to which the photosensitizer is attached. The synthesized organic layers were characterized by means of cyclic voltammetry, XPS and Raman Spectroscopy. It was shown that the phenothiazines immobilized via proposed strategy retain their photochemical properties and are able to generate 1O2 when activated by the laser radiation. The effectiveness of in situ singlet oxygen generation by those new solid photoactive materials was determined by means of UVVis spectroscopy. The reported, covalently modified solid surfaces may find their application as the singlet oxygen photogenerators in the fine chemicals' synthesis or in the wastewater treatment.

  18. Electrochemical detection of point mutation based on surface ligation reaction and biometallization.

    PubMed

    Zhang, Peng; Chu, Xia; Xu, Xiangmin; Shen, Guoli; Yu, Ruqin

    2008-05-15

    A highly sensitive electrochemical method for point mutation detection based on surface enzymatic ligation reaction and biometallization is demonstrated. In this method the surface-immobilized allele-specific probe, complementary to the mutant target, undergoes allele-specific ligation with the 5'-phosphorylated ligation probe in the presence of the mutant oligonucleotide target and E. coli DNA ligase. If there is an allele mismatch, no ligation takes place. After thermal treatment at 90 degrees C, the formed duplex melts apart, which merely allows the ligation product to remain on the electrode surface. Then, biotinylated detection probes hybridize with the ligation product. With the binding of streptavidin-alkaline phosphatase (SA-ALP) to the biotinylated probes, a non-reductive substrate of alkaline phosphatase, ascorbic acid 2-phosphate (AA-P), can be converted into ascorbic acid (AA) at the electrode surface. Silver ions in solution are then reduced by AA, resulting in the deposition of silver metal onto the electrode surface. Linear sweep voltammetry (LSV) is used to detect the amount of deposited silver. The proposed approach has been successfully implemented for the identification of single base mutation in codon 12 of K-ras oncogene target with a detection limit of 80fM, demonstrating that this method provides a highly specific, sensitive and cost-efficient approach for point mutation detection.

  19. Preparation of multi-functional superhydrophobic lanthanum surface on carbon steel via facile electrochemical method

    NASA Astrophysics Data System (ADS)

    Chen, Xi; He, Yi; Fan, Yi; Yang, Qiangbin; Li, Han

    2016-12-01

    We have constructed a superhydrophobic surface with lanthanum palmitate on carbon steel via a facile one-step electrodeposition. The morphology and chemical composition of the superhydrophobic surface were characterized by field-emission scanning electron microscopy with attached energy dispersive X-ray spectrum, Fourier transform infrared spectra and X-ray photoelectron spectroscopy, respectively. The as-prepared surface with hierarchical structure has a largest contact angle of 160° ± 0.5° and a lowest sliding angle of 2° ± 0.5°. We found that both high electrodeposition potential and high concentrations lanthanum nitrate can accelerate the formation of superhydrophobic film. The electrochemical measurements demonstrated that the superhydrophobic surface exhibited excellent anti-corrosion performance in 3.5 wt% NaCl solution. Moreover, we also investigated the chemical stability, self-cleaning and oil/water separation of the superhydrophobic film. We believe that the facile fabrication method provides a promising strategy to fabricate multi-functional superhydrophobic surface with lanthanide series rare-earth elements on kinds of substrates.

  20. Optical and electrochemical properties of ordered macroporous gold array on the ITO surface

    NASA Astrophysics Data System (ADS)

    Lu, Huidan; Liu, Yongping; Han, Guo-Cheng

    2011-06-01

    The electrochemical and optical properties of transparent, two-dimensional macroporous gold film were investigated. Colloidal crystal templates were assembled onto indium-doped tin oxide (ITO) glass surface through vertical depositing method. Following gold electrodeposition, they were removed by dissolution with tetrahydrofuran (THF). The highly ordered macroporous gold array was achieved. It was characterized by scanning electron microscope (SEM) and ultraviolet visible (UV-vis) spectrophotometry. The optical transparency of the gold film was near 25% and fairly constant between 300 and 900 nm. The macroporous gold film electrode was mounted into a thin-layer transmission cell. The electrochemical response was evaluated by thin-layer cyclic voltammograms (CV) of the Fe (CN) 63-/Fe (CN) 64- couple. Thin-layer cell exhibits good shape of waves and nearly symmetric cathodic and anodic waves. E0' value and n of TMPD + rad /TMPD (TMPD is acronyms for N,N,N',N'-tetramethyl-p-phenylenediamine, and TMPD + rad is its mono-cation radical) couple were determined. Furthermore, results demonstrated electrolytic equilibrium was faster reached in macroporous gold film than ITO electrode.

  1. Multi-resistive reduced graphene oxide diode with reversible surface electrochemical reaction induced carrier control.

    PubMed

    Seo, Hyungtak; Ahn, Seungbae; Kim, Jinseo; Lee, Young-Ahn; Chung, Koo-Hyun; Jeon, Ki-Joon

    2014-07-10

    The extended application of graphene-based electronic devices requires a bandgap opening in order to realize the targeted device functionality. Since the bandgap tuning of pristine graphene is limited to 360 meV, the chemical modification of graphene is considered essential to achieve a large bandgap opening at the expense of electrical properties degradation. Reduced graphene oxide (RGO) has attracted significant interest for fabricating graphene-based semiconductors since it has several advantages over other forms of chemically modified graphene; such as tunable bandgap opening, decent electrical properties, and easy synthesis. Because of the reduced bonding nature of RGO, the role of metastable oxygen in the RGO matrix is recently highlighted and it may offer emerging ionic devices. In this study, we show that multi-resistivity RGO/n-Si diodes can be obtained by controlling the RGO thickness at a nanometer scale. This is made possible by (1) a metastable lattice-oxygen drift within bulk RGO and (2) electrochemical ambient hydroxyl (OH) formation at the RGO surface. The effect demonstrated in a p-RGO/n-Si heterojunction diode is equivalent to electrochemically driven reversible electronic manipulation and therefore provides an important basis for the application of O bistability in RGO for chemical sensors and electrocatalysis.

  2. Surface electrochemical control for fine coal and pyrite separation. Final report

    SciTech Connect

    Wadsworth, M.E.; Bodily, D.M.; Hu, Weibai; Chen, Wanxiong; Huang, Qinping; Liang, Jun; Riley, A.M.; Li, Jun; Wann, Jyi-Perng; Zhong, Tingke; Zhu, Ximeng

    1993-01-20

    Laboratory flotation tests were carried out on three coals and on coal pyrite. Floatability measurements included natural floatability, flotation with a xanthate collector and salt flotation. The ranking of the floatability of the three coals were: Upper Freeport > Pittsburgh > Illinois. The floatability of mineral pyrite and coal pyrite increased markedly with xanthate concentration, but decreased with increased pH. In general, coal pyrite was more difficult to float than mineral pyrite. This was attributed to the presence of surface carbonaceous and mineral matter, since floatability of coal pyrite improved by acid pretreatment. Flotation tests demonstrated that the floatability of coal and mineral pyrite was greatly enhanced by the presence of an electrolyte. Flotation was also enhanced by the addition of modifiers such as CuSO{sub 4}, Na{sub 2}S, CO{sub 2} and EDTA. Lime additions markedly reduced the floatability of coal pyrite. Enhanced floatability of coal pyrite resulted when the pyrite was anodically oxidized in a specially constructed electrochemical flotation cell Pretreatment in potential ranges previously observed for polysulfide and sulfur film formation resulted in the enhanced floatability. While interesting trends and influences, both chemical and electrochemical, markedly improved the floatability of coal, there is little hope for reverse flotation as an effective technology for coal/coal-pyrite separations. The effects of poor liberation and entrainment appear overriding.

  3. Multi-resistive Reduced Graphene Oxide Diode with Reversible Surface Electrochemical Reaction induced Carrier Control

    PubMed Central

    Seo, Hyungtak; Ahn, Seungbae; Kim, Jinseo; Lee, Young-Ahn; Chung, Koo-Hyun; Jeon, Ki-Joon

    2014-01-01

    The extended application of graphene-based electronic devices requires a bandgap opening in order to realize the targeted device functionality. Since the bandgap tuning of pristine graphene is limited to 360 meV, the chemical modification of graphene is considered essential to achieve a large bandgap opening at the expense of electrical properties degradation. Reduced graphene oxide (RGO) has attracted significant interest for fabricating graphene-based semiconductors since it has several advantages over other forms of chemically modified graphene; such as tunable bandgap opening, decent electrical properties, and easy synthesis. Because of the reduced bonding nature of RGO, the role of metastable oxygen in the RGO matrix is recently highlighted and it may offer emerging ionic devices. In this study, we show that multi-resistivity RGO/n-Si diodes can be obtained by controlling the RGO thickness at a nanometer scale. This is made possible by (1) a metastable lattice-oxygen drift within bulk RGO and (2) electrochemical ambient hydroxyl (OH) formation at the RGO surface. The effect demonstrated in a p-RGO/n-Si heterojunction diode is equivalent to electrochemically driven reversible electronic manipulation and therefore provides an important basis for the application of O bistability in RGO for chemical sensors and electrocatalysis. PMID:25007942

  4. Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

    PubMed

    Luca, Oana R; Fenwick, Aidan Q

    2015-11-01

    The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination.

  5. Novel electrochemical redox-active species: one-step synthesis of polyaniline derivative-Au/Pd and its application for multiplexed immunoassay

    NASA Astrophysics Data System (ADS)

    Wang, Liyuan; Feng, Feng; Ma, Zhanfang

    2015-11-01

    Electrochemical redox-active species play crucial role in electrochemically multiplexed immunoassays. A one-pot method for synthesizing four kinds of new electrochemical redox-active species was reported using HAuCl4 and Na2PdCl4 as dual oxidating agents and aniline derivatives as monomers. The synthesized polyaniline derivative-Au/Pd composites, namely poly(N-methyl-o-benzenediamine)-Au/Pd, poly(N-phenyl-o-phenylenediamine)-Au/Pd, poly(N-phenyl-p-phenylenediamine)-Au/Pd and poly(3,3’,5,5’-tetramethylbenzidine)-Au/Pd, exhibited electrochemical redox activity at -0.65 V, -0.3 V, 0.12 V, and 0.5 V, respectively. Meanwhile, these composites showed high H2O2 electrocatalytic activity because of the presence of Au/Pd. The as-prepared composites were used as electrochemical immunoprobes in simultaneous detection of four tumor biomarkers (carcinoembryonic antigen (CEA), carbohydrate antigen 19-9 (CA199), carbohydrate antigen 72-4 (CA724), and alpha fetoprotein (AFP)). This immunoassay shed light on potential applications in simultaneous gastric cancer (related biomarkers: CEA, CA199, CA724) and liver cancer diagnosis (related biomarkers: CEA, CA199, AFP). The present strategy to the synthesize redox species could be easily extended to other polymers such as polypyrrole derivatives and polythiophene derivatives. This would be of great significance in the electrochemical detection of more analytes.

  6. Novel electrochemical redox-active species: one-step synthesis of polyaniline derivative-Au/Pd and its application for multiplexed immunoassay.

    PubMed

    Wang, Liyuan; Feng, Feng; Ma, Zhanfang

    2015-11-18

    Electrochemical redox-active species play crucial role in electrochemically multiplexed immunoassays. A one-pot method for synthesizing four kinds of new electrochemical redox-active species was reported using HAuCl4 and Na2PdCl4 as dual oxidating agents and aniline derivatives as monomers. The synthesized polyaniline derivative-Au/Pd composites, namely poly(N-methyl-o-benzenediamine)-Au/Pd, poly(N-phenyl-o-phenylenediamine)-Au/Pd, poly(N-phenyl-p-phenylenediamine)-Au/Pd and poly(3,3',5,5'-tetramethylbenzidine)-Au/Pd, exhibited electrochemical redox activity at -0.65 V, -0.3 V, 0.12 V, and 0.5 V, respectively. Meanwhile, these composites showed high H2O2 electrocatalytic activity because of the presence of Au/Pd. The as-prepared composites were used as electrochemical immunoprobes in simultaneous detection of four tumor biomarkers (carcinoembryonic antigen (CEA), carbohydrate antigen 19-9 (CA199), carbohydrate antigen 72-4 (CA724), and alpha fetoprotein (AFP)). This immunoassay shed light on potential applications in simultaneous gastric cancer (related biomarkers: CEA, CA199, CA724) and liver cancer diagnosis (related biomarkers: CEA, CA199, AFP). The present strategy to the synthesize redox species could be easily extended to other polymers such as polypyrrole derivatives and polythiophene derivatives. This would be of great significance in the electrochemical detection of more analytes.

  7. Novel electrochemical redox-active species: one-step synthesis of polyaniline derivative-Au/Pd and its application for multiplexed immunoassay

    PubMed Central

    Wang, Liyuan; Feng, Feng; Ma, Zhanfang

    2015-01-01

    Electrochemical redox-active species play crucial role in electrochemically multiplexed immunoassays. A one-pot method for synthesizing four kinds of new electrochemical redox-active species was reported using HAuCl4 and Na2PdCl4 as dual oxidating agents and aniline derivatives as monomers. The synthesized polyaniline derivative-Au/Pd composites, namely poly(N-methyl-o-benzenediamine)-Au/Pd, poly(N-phenyl-o-phenylenediamine)-Au/Pd, poly(N-phenyl-p-phenylenediamine)-Au/Pd and poly(3,3’,5,5’-tetramethylbenzidine)-Au/Pd, exhibited electrochemical redox activity at −0.65 V, −0.3 V, 0.12 V, and 0.5 V, respectively. Meanwhile, these composites showed high H2O2 electrocatalytic activity because of the presence of Au/Pd. The as-prepared composites were used as electrochemical immunoprobes in simultaneous detection of four tumor biomarkers (carcinoembryonic antigen (CEA), carbohydrate antigen 19-9 (CA199), carbohydrate antigen 72-4 (CA724), and alpha fetoprotein (AFP)). This immunoassay shed light on potential applications in simultaneous gastric cancer (related biomarkers: CEA, CA199, CA724) and liver cancer diagnosis (related biomarkers: CEA, CA199, AFP). The present strategy to the synthesize redox species could be easily extended to other polymers such as polypyrrole derivatives and polythiophene derivatives. This would be of great significance in the electrochemical detection of more analytes. PMID:26577799

  8. Deterministic analysis of processes at corroding metal surfaces and the study of electrochemical noise in these systems

    SciTech Connect

    Latanision, R.M.

    1990-12-01

    Electrochemical corrosion is pervasive in virtually all engineering systems and in virtually all industrial circumstances. Although engineers now understand how to design systems to minimize corrosion in many instances, many fundamental questions remain poorly understood and, therefore, the development of corrosion control strategies is based more on empiricism than on a deep understanding of the processes by which metals corrode in electrolytes. Fluctuations in potential, or current, in electrochemical systems have been observed for many years. To date, all investigations of this phenomenon have utilized non-deterministic analyses. In this work it is proposed to study electrochemical noise from a deterministic viewpoint by comparison of experimental parameters, such as first and second order moments (non-deterministic), with computer simulation of corrosion at metal surfaces. In this way it is proposed to analyze the origins of these fluctuations and to elucidate the relationship between these fluctuations and kinetic parameters associated with metal dissolution and cathodic reduction reactions. This research program addresses in essence two areas of interest: (a) computer modeling of corrosion processes in order to study the electrochemical processes on an atomistic scale, and (b) experimental investigations of fluctuations in electrochemical systems and correlation of experimental results with computer modeling. In effect, the noise generated by mathematical modeling will be analyzed and compared to experimental noise in electrochemical systems. 1 fig.

  9. Electrochemical impedance spectroscopy studies of organic-solvent-induced permeability changes in nanoporous films derived from a cylinder-forming diblock copolymer.

    PubMed

    Perera, D M Neluni T; Pandey, Bipin; Ito, Takashi

    2011-09-06

    In this paper we report electrochemical investigations of the influence of organic solvents dissolved in aqueous solution on the permeability of nanoporous films derived from a cylinder-forming polystyrene-poly(methyl methacrylate) diblock copolymer (CF-PS-b-PMMA). The nanoporous films (ca. 30 nm in pore diameter) were prepared on planar gold electrodes via UV-based degradation of the cylindrical PMMA domains of annealed CF-PS-b-PMMA films (30-45 nm thick). The permeability of the electrode-supported nanoporous films was assessed using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The faradic current of Fe(CN)(6)(3-/4-) decreased upon immersion in aqueous solutions saturated with toluene or methylene chloride (5.8 mM and 0.20 M, respectively). EIS data indicated that the decrease in faradic current mainly reflected an increase in the pore resistance (R(pore)). In contrast, R(pore) did not change in a saturated n-heptane solution, 0.17 M ethanol, or 5.8 mM aqueous solutions of methylene chloride, diethyl ether, methyl ethyl ketone, or ethanol. Atomic force microscopy images of a nanoporous film in aqueous solution with and without 5.8 mM toluene showed a reversible change in the surface morphology, which was consistent with a toluene-induced change in R(pore). The solvent-induced increase in R(pore) was attributed to the swelling of the nanoporous films by the organic solvents, which decreased the effective pore diameter. The reversible permeability changes suggest that the surface of CF-PS-b-PMMA-derived nanoporous films can be functionalized in organic environments without destroying the nanoporous structure. In addition, the solvent-induced swelling may provide a simple means for controlling the permeability of such nanoporous films.

  10. Effect of gold immersion time on the electrochemical migration property of electroless nickel/immersion gold surface finishing.

    PubMed

    Bui, Q V; Yoon, Jeong-Won; Jung, Seung-Boo

    2012-04-01

    In this study, the electrochemical performance of an electroless nickel/immersion gold (ENIG) surface finish was evaluated as a function of the Au immersion time by the water immersion migration test. As the Au plating time increased, the electroless nickel phosphorous (EN-P) changed from amorphous to crystalline and then increased in crystallinity. X-ray diffraction (XRD) was used to evaluate the crystallinity of the plating layer. The electrical resistance of the electrodes was tracked as the sample was immersed in water with a 5 V bias. The microstructures of the electrodes after the electrochemical migration test were observed by using secondary electron microscopy (SEM) and energy dispersive spectroscopy (EDS). As the Au immersion time increased, the EN-P's crystallinity and Au thickness increased. This enhanced the electrochemical migration protection of the surface finish layer.

  11. Deriving Albedo from Coupled MERIS and MODIS Surface Products

    NASA Technical Reports Server (NTRS)

    Gao, Feng; Schaaf, Crystal; Jin, Yu-Fang; Lucht, Wolfgang; Strahler, Alan

    2004-01-01

    MERIS Level 2 surface reflectance products are now available to the scientific community. This paper demonstrates the production of MERIS-derived surface albedo and Nadir Bidirectional Reflectance Distribution Function (BRDF) adjusted reflectances by coupling the MERIS data with MODIS BRDF products. Initial efforts rely on the specification of surface anisotropy as provided by the global MODIS BRDF product for a first guess of the shape of the BRDF and then make use all of the coincidently available, partially atmospherically corrected, cloud cleared, MERIS observations to generate MERIS-derived BRDF and surface albedo quantities for each location. Comparisons between MODIS (aerosol-corrected) and MERIS (not-yet aerosol-corrected) surface values from April and May 2003 are also presented for case studies in Spain and California as well as preliminary comparisons with field data from the Devil's Rock Surfrad/BSRN site.

  12. Quantification of photoelectrogenerated hydroxyl radical on TiO2 by surface interrogation scanning electrochemical microscopy.

    PubMed

    Zigah, Dodzi; Rodríguez-López, Joaquín; Bard, Allen J

    2012-10-05

    The surface interrogation mode of scanning electrochemical microscopy (SI-SECM) was used for the detection and quantification of adsorbed hydroxyl radical ˙OH((ads)) generated photoelectrochemically at the surface of a nanostructured TiO(2) substrate electrode. In this transient technique, a SECM tip is used to generate in situ a titrant from a reversible redox pair that reacts with the adsorbed species at the substrate. This reaction produces an SECM feedback response from which the amount of adsorbate and its decay kinetics can be obtained. The redox pair IrCl(6)(2-/3-) offered a reactive, selective and stable surface interrogation agent under the strongly oxidizing conditions of the photoelectrochemical cell. A typical ˙OH((ads)) saturation coverage of 338 μC cm(-2) was found in our nanostructured samples by its reduction with the electrogenerated IrCl(6)(3-). The decay kinetics of ˙OH((ads)) by dimerization to produce H(2)O(2) were studied through the time dependence of the SI-SECM signal and the surface dimerization rate constant was found to be ~k(OH) = 2.2 × 10(3) mol(-1) m(2) s(-1). A radical scavenger, such as methanol, competitively consumes ˙OH((ads)) and yields a shorter SI-SECM transient, where a pseudo-first order rate analysis at 2 M methanol yields a decay constant of k'(MeOH) ~ 1 s(-1).

  13. Electrochemically assisted deposition of strontium modified magnesium phosphate on titanium surfaces.

    PubMed

    Meininger, M; Wolf-Brandstetter, C; Zerweck, J; Wenninger, F; Gbureck, U; Groll, J; Moseke, C

    2016-10-01

    Electrochemically assisted deposition was utilized to produce ceramic coatings on the basis of magnesium ammonium phosphate (struvite) on corundum-blasted titanium surfaces. By the addition of defined concentrations of strontium nitrate to the coating electrolyte Sr(2+) ions were successfully incorporated into the struvite matrix. By variation of deposition parameters it was possible to fabricate coatings with different kinetics of Sr(2+) into physiological media, whereas the release of therapeutically relevant strontium doses could be sustained over several weeks. Morphological and crystallographic examinations of the immersed coatings revealed that the degradation of struvite and the release of Sr(2+) ions were accompanied by a transformation of the coating to a calcium phosphate based phase similar to low-crystalline hydroxyapatite. These findings showed that strontium doped struvite coatings may provide a promising degradable coating system for the local application of strontium or other biologically active metal ions in the implant-bone interface.

  14. Effects of surface tension and electrochemical reactions in Li-ion battery electrode nanoparticles

    NASA Astrophysics Data System (ADS)

    Stein, Peter; Zhao, Ying; Xu, Bai-Xiang

    2016-11-01

    The size- and shape-dependency of the chemo-mechanical behavior of spherical and ellipsoidal nanoparticles in Li-ion battery electrodes are investigated by a stress-assisted diffusion model and 3D finite element simulations. The model features surface tension, a direct coupling between diffusion and elasticity, concentration-dependent diffusivity, and a Butler-Volmer relation for the description of electrochemical reactions that is modified to account for mechanical effects. Simulation results on spherical particles reveal that surface tension causes additional pressure fields in the particles, shifting the stress state towards the compressive regime. This provides mechanical stabilization, allowing, in principle, for higher charge/discharge rates. However, due to this pressure the attainable lithiation for a given potential difference is reduced during insertion, whereas a higher amount of ions is given off during extraction. Ellipsoidal particles with an aspect ratio deviating from that of a sphere with the same volume expose a larger surface area to the intercalation reactions. Consequently, they exhibit accelerated (dis)charge rates. However, due to the enhanced pressure in regions with high curvature, the accessible capacity of ellipsoidal particles is less than that of spherical particles.

  15. Surface science and electrochemical studies of metal-modified carbides for fuel cells and hydrogen production

    NASA Astrophysics Data System (ADS)

    Kelly, Thomas Glenn

    Carbides of the early transition metals have emerged as low-cost catalysts that are active for a wide range of reactions. The surface chemistry of carbides can be altered by modifying the surface with small amounts of admetals. These metal-modified carbides can be effective replacements for Pt-based bimetallic systems, which suffer from the drawbacks of high cost and low thermal stability. In this dissertation, metal-modified carbides were studied for reactions with applications to renewable energy technologies. It is demonstrated that metal-modified carbides possess high activity for alcohol reforming and electrochemical hydrogen production. First, the surface chemistry of carbides towards alcohol decomposition is studied using density functional theory (DFT) and surface science experiments. The Vienna Ab initio Simulation Package (VASP) was used to calculate the binding energies of alcohols and decomposition intermediates on metal-modified carbides. The calculated binding energies were then correlated to reforming activity determined experimentally using temperature programmed desorption (TPD). In the case of methanol decomposition, it was found that tungsten monocarbide (WC) selectively cleaved the C-O bond to produce methane. Upon modifying the surface with a single layer of metal such as Ni, Pt, or Rh, the selectivity shifted towards scission of the C-H bonds while leaving the C-O bond intact, producing carbon monoxide (CO) and H2. High resolution energy loss spectroscopy (HREELS) was used to examine the bond breaking sequence as a function of temperature. From HREELS, it was shown that the surfaces followed an activity trend of Rh > Ni > Pt. The Au-modified WC surface possessed too low of a methanol binding energy, and molecular desorption of methanol was the most favorable pathway on this surface. Next, the ability of Rh-modified WC to break the C-C bond of C2 and C3 alcohols was demonstrated. HREELS showed that ethanol decomposed through an acetaldehyde

  16. Highly sensitive electrochemical sensor for chloramphenicol based on MOF derived exfoliated porous carbon.

    PubMed

    Xiao, Lili; Xu, Ruiyu; Yuan, Qunhui; Wang, Fu

    2017-05-15

    Benefit from the advantages in costless, simplicity and efficiency, solvent exfoliation has been widely used in preparation of two-dimensional nanosheets with enhanced performances in electronics, photonics, and catalysis. In this work, solvent exfoliation was first applied to prepare exfoliated porous carbon (EPC) from an isoreticular metal-organic framework-8 (IRMOF-8) derived porous carbon (DPC). The obtained EPC with high surface area (1854m(2)g(-1)) and improved dispersibility was used as electrode modifier for glassy carbon electrode (GCE) in square wave voltammetry (SWV) detection of chloramphenicol (CAP). The sensitivity of EPC modified GCE (EPC/GCE) was greatly improved in compare with that of the DPC modification. The corresponding linear ranges are 1×10(-8)-1×10(-6)molL(-1) and 1×10(-6)-4×10(-6)molL(-1). The detection limit was calculated to be 2.9×10(-9)molL(-1) (at a signal-to-noise ratio of 3, S/N=3). In addition, the proposed sensor was successfully applied in the analysis of CAP in honey and achieved satisfying recovery.

  17. The MIL-88A-Derived Fe3O4-Carbon Hierarchical Nanocomposites for Electrochemical Sensing

    NASA Astrophysics Data System (ADS)

    Wang, Li; Zhang, Yayun; Li, Xia; Xie, Yingzhen; He, Juan; Yu, Jie; Song, Yonghai

    2015-09-01

    Metal or metal oxides/carbon nanocomposites with hierarchical superstructures have become one of the most promising functional materials in sensor, catalysis, energy conversion, etc. In this work, novel hierarchical Fe3O4/carbon superstructures have been fabricated based on metal-organic frameworks (MOFs)-derived method. Three kinds of Fe-MOFs (MIL-88A) with different morphologies were prepared beforehand as templates, and then pyrolyzed to fabricate the corresponding novel hierarchical Fe3O4/carbon superstructures. The systematic studies on the thermal decomposition process of the three kinds of MIL-88A and the effect of template morphology on the products were carried out in detail. Scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy and thermal analysis were employed to investigate the hierarchical Fe3O4/carbon superstructures. Based on these resulted hierarchical Fe3O4/carbon superstructures, a novel and sensitive nonenzymatic N-acetyl cysteine sensor was developed. The porous and hierarchical superstructures and large surface area of the as-formed Fe3O4/carbon superstructures eventually contributed to the good electrocatalytic activity of the prepared sensor towards the oxidation of N-acetyl cysteine. The proposed preparation method of the hierarchical Fe3O4/carbon superstructures is simple, efficient, cheap and easy to mass production. It might open up a new way for hierarchical superstructures preparation.

  18. The MIL-88A-Derived Fe3O4-Carbon Hierarchical Nanocomposites for Electrochemical Sensing

    PubMed Central

    Wang, Li; Zhang, Yayun; Li, Xia; Xie, Yingzhen; He, Juan; Yu, Jie; Song, Yonghai

    2015-01-01

    Metal or metal oxides/carbon nanocomposites with hierarchical superstructures have become one of the most promising functional materials in sensor, catalysis, energy conversion, etc. In this work, novel hierarchical Fe3O4/carbon superstructures have been fabricated based on metal-organic frameworks (MOFs)-derived method. Three kinds of Fe-MOFs (MIL-88A) with different morphologies were prepared beforehand as templates, and then pyrolyzed to fabricate the corresponding novel hierarchical Fe3O4/carbon superstructures. The systematic studies on the thermal decomposition process of the three kinds of MIL-88A and the effect of template morphology on the products were carried out in detail. Scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy and thermal analysis were employed to investigate the hierarchical Fe3O4/carbon superstructures. Based on these resulted hierarchical Fe3O4/carbon superstructures, a novel and sensitive nonenzymatic N-acetyl cysteine sensor was developed. The porous and hierarchical superstructures and large surface area of the as-formed Fe3O4/carbon superstructures eventually contributed to the good electrocatalytic activity of the prepared sensor towards the oxidation of N-acetyl cysteine. The proposed preparation method of the hierarchical Fe3O4/carbon superstructures is simple, efficient, cheap and easy to mass production. It might open up a new way for hierarchical superstructures preparation. PMID:26387535

  19. Electrochemical investigations of 3-(3-thienyl) acrylic acid protected nanoclusters and planar gold surfaces.

    PubMed

    Nirmal, R G; Kavitha, A L; Berchmans, Sheela; Yegnaraman, V

    2007-06-01

    Formation of self assembled monolayers on gold surface by thiols and disulphides is a well known phenomenon and extensive research work has been carried out in this area with envisaged applications in the area of sensors, molecular electronics, lithography, device fabrication using bottom-up approach, etc. Recently, it has been established that thiophene molecules can self assemble on gold surface due to Au-S interactions. 3-(3-thienyl) acrylic acid, a bifunctional ligand is used in this work to form self-assembled monolayers on planar gold surfaces (two dimensional assemblies) and to prepare monolayer protected gold nano clusters (three-dimensional assemblies). The electron transfer blocking properties of the two-dimensional monolayers were evaluated by using standard redox probes like ferrocyanide anions and Ruthenium hexamine cations. The functionalisation of the two-dimensional and three-dimensional assemblies has been carried out with ferrocene carboxylic acid and the functionalised monolayers were characterized by Cyclic voltammetry. The formation of thienyl acrylic acid protected nanoclusters has been verified by TEM and surface plasmon resonance absorption. It has been observed that when thiophene based ligands are used as stabilizers for the formation of metal nanoparticles, they tend to aggregate as a result of pi-pi interactions between adjacent thiophene ligands. In this case it is found that aggregation is prevented. The substituent at the thiophene ring hinders pi-pi interactions. The quantised nature of electrochemical charging of these nanoparticles has been demonstrated by differential pulse voltammetry (DPV), which exhibit peak like features (coulomb's staircase). This work also explores the possibility of using 3-(3-thienyl) acrylic acid as building blocks or spacers on planar and colloidal gold surfaces for potential applications in the field of sensors and devices.

  20. Improvement of electrochemical activity of LiMnPO4-based cathode by surface iron enrichment

    NASA Astrophysics Data System (ADS)

    Xu, Xiaoyue; Wang, Tao; Bi, Yujing; Liu, Meng; Yang, Wenchao; Peng, Zhe; Wang, Deyu

    2017-02-01

    LiMnPO4 has attracted massive interests due to its appropriate redox potential and the success of its iron comparative in the lithium ion batteries. The bulk substitution has been widely used to address the poor electrochemical activity of LiMnPO4, which is much lower than that of LiFePO4. In this work, we compare the performance of the core-shell structure and the homogeneous substitution with the same Mn/Fe molar ratio of LiMn0.8Fe0.2PO4. The core-shell phosphate material after carbon coating is composed of a core part of quasi-single LiMnPO4 phase, and a 3-4 nm shell layer of quasi-single LiFePO4-phase, separated by the phase boundary with 1-2 nm thickness. It is interesting to reveal that the core-shell samples exhibit capacities of 156.4, 144.5, 128.2 mAh g-1 under 0.1C, 1C and 5C respectively, which are 5-10% higher than that of the homogenous substituted LiMn0.8Fe0.2PO4 at the corresponding rates, while both of these samples present excellent cyclic stability, still retaining ∼95% of the initial capacities after 1000 cycles under 1C discharging rate. Our results demonstrate that the main reason for LiMnPO4's poor electrochemical activity should be emphasized on the surface polarization, whereas the tardiness on bulk transportation is not as serious as it was presumed.

  1. Scanning tunneling microscopy of electrochemically activated platinum surfaces. A direct ex-situ determination of the electrode nanotopography

    SciTech Connect

    Vazquez, L.; Gomez, J.; Baro, A.M.; Garcia, N.; Marcos, M.L.; Velasco, J.G.; Vara, J.M.; Arvia, A.J.; Presa, J.; Garcia, A.; Aguilar, M.

    1987-03-18

    A direct scanning tunneling microscopy ex-situ determination on the nanometer scale of the topography of electrochemically highly activated platinum electrodes is presented. A correlation between catalytic activity and surface microtopography becomes evident. This result gives support to a structural model for the activated electrode surface. In the model, a volume with a pebble-like structure allows electrocatalytic processes to occur practically free of diffusion relaxation contributions under usual voltammetric conditions.

  2. Surface analytical and electrochemical studies of aircraft alloy pretreatments and their influence on corrosion

    NASA Astrophysics Data System (ADS)

    Kagwade, Sanjay Vasudeo

    Current research in the areas of aircraft alloy pretreatments and their influence on corrosion have raised fundamental questions regarding the applicability of standard surface preparation and analyzing protocols. Electrochemical techniques along with surface analytical techniques such as Laser Speckle Sensor and X-ray Photoelectron Spectroscopy have demonstrated the ability to detect early pitting corrosion in aluminum alloy AA2024-T3. The ASTM E1078-85 cleaning protocol recommends the use of acetone as an organic solvent. In the presence of ambient light, water vapor and copper; acetone reacts slowly to form acetic acid, which corrodes the copper surface. This reaction is completely inhibited in darkness, suggesting that copper is acting photocatalytically for the reaction between acetone and water. Acetone degreasing of AA2024-T3 following the ASTM E1078-85 protocol shows a similar effect on copper intermetallics. In the presence of a mist of sodium chloride solution and ambient light, the so formed acetic acid with the chloride solution layer supports severe pitting corrosion of the intermetallic particles. Additionally, there is evidence showing the deposition of dissolved metallic copper on the aluminum matrix. The pitting attack in sodium chloride was inhibited in darkness, suggesting that the slow reaction of the surface adsorbed acetone with water was prevented. Corrosion-fatigue studies showed the lowering of the total fatigue life of the alloy in a sodium chloride solution, with prior exposure to acetone. Widely used surface preparation techniques on AA2024-T3, based on electrochemical and abrasive polishing techniques showed the modification of the alloy surface. Copper enrichment of the surface was observed in all the samples. A surface preparation protocol based on mechanical polishing with copper-free alumina suspensions has been recommended. X-ray Photoelectron Spectroscopy characterization of hexavalent chromium in the presence of trivalent

  3. A combined "electrochemical-frustrated lewis pair" approach to hydrogen activation: surface catalytic effects at platinum electrodes.

    PubMed

    Lawrence, Elliot J; Blagg, Robin J; Hughes, David L; Ashley, Andrew E; Wildgoose, Gregory G

    2015-01-07

    Herein, we extend our "combined electrochemical-frustrated Lewis pair" approach to include Pt electrode surfaces for the first time. We found that the voltammetric response of an electrochemical-frustrated Lewis pair (FLP) system involving the B(C6 F5 )3 /[HB(C6 F5 )3 ](-) redox couple exhibits a strong surface electrocatalytic effect at Pt electrodes. Using a combination of kinetic competition studies in the presence of a H atom scavenger, 6-bromohexene, and by changing the steric bulk of the Lewis acid borane catalyst from B(C6 F5 )3 to B(C6 Cl5 )3 , the mechanism of electrochemical-FLP reactions on Pt surfaces was shown to be dominated by hydrogen-atom transfer (HAT) between Pt, [PtH] adatoms and transient [HB(C6 F5 )3 ](⋅) electrooxidation intermediates. These findings provide further insight into this new area of combining electrochemical and FLP reactions, and proffers additional avenues for exploration beyond energy generation, such as in electrosynthesis.

  4. A Combined "Electrochemical-Frustrated Lewis Pair" Approach to Hydrogen Activation: Surface Catalytic Effects at Platinum Electrodes.

    PubMed

    Lawrence, Elliot J; Blagg, Robin J; Hughes, David L; Ashley, Andrew E; Wildgoose, Gregory G

    2014-11-06

    Herein, we extend our "combined electrochemical-frustrated Lewis pair" approach to include Pt electrode surfaces for the first time. We found that the voltammetric response of an electrochemical-frustrated Lewis pair (FLP) system involving the B(C6 F5 )3 /[HB(C6 F5 )3 ](-) redox couple exhibits a strong surface electrocatalytic effect at Pt electrodes. Using a combination of kinetic competition studies in the presence of a H atom scavenger, 6-bromohexene, and by changing the steric bulk of the Lewis acid borane catalyst from B(C6 F5 )3 to B(C6 Cl5 )3 , the mechanism of electrochemical-FLP reactions on Pt surfaces was shown to be dominated by hydrogen-atom transfer (HAT) between Pt, [PtH] adatoms and transient [HB(C6 F5 )3 ](⋅) electrooxidation intermediates. These findings provide further insight into this new area of combining electrochemical and FLP reactions, and proffers additional avenues for exploration beyond energy generation, such as in electrosynthesis.

  5. Photoresponsive cellulose fibers by surface modification with multifunctional cellulose derivatives.

    PubMed

    Grigoray, Olga; Wondraczek, Holger; Heikkilä, Elina; Fardim, Pedro; Heinze, Thomas

    2014-10-13

    Eucalyptus bleached kraft pulp fibers were modified by adsorption of novel bio-based multifunctional cellulose derivatives in order to generate light responsive surfaces. The cellulose derivatives used were decorated with both cationic groups (degree of substitution, DS of 0.34) and photoactive groups (DS of 0.11 and 0.37). The adsorption was studied by UV-vis spectroscopy, surface plasmon resonance (SPR) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). The adsorption isotherms followed the Freundlich model and it turned out that the main driving force for the adsorption was electrostatic interaction. Moreover, strong indications for hydrophobic interactions between the fibers and the derivatives and the derivatives themselves were found. ToF-SIMS imaging revealed an even distribution of the derivatives on the fiber surfaces. The modified fibers underwent fast photocrosslinking under UV-irradiation as demonstrated by light absorbance and fluorescence measurements. Thus, our results proved that the modified fibers exhibited light-responsive properties and can potentially be used for the manufacture of smart bio-based materials.

  6. Satellite Derived Land Surface Temperature for Model Assimilation

    NASA Technical Reports Server (NTRS)

    Suggs, Ronnie J.; Jedlovec, Gary J.; Lapenta, William

    1999-01-01

    Studies have shown that land surface temperature (LST) tendencies are sensitive to the surface moisture availability which is a function of soil moisture and vegetation. The assimilation of satellite derived LST tendencies into the surface energy budget of mesoscale models has shown promise in improving the representation of the complex effects of both soil moisture and vegetation within the models for short term simulations. LST derived from geostationary satellites has the potential of providing the temporal and spatial resolution needed for an LST assimilation process. This paper presents an analysis comparing the LST derived from GOES-8 infrared measurements with LST calculated by the MM5 numerical model. The satellite derived LSTs are calculated using a physical split window approach using channels 4 and 5 of GOES-8. The differences in the LST data sets, especially the tendencies, are presented and examined. Quantifying the differences between the data sets provide insight of possible weaknesses in the model parameterizations affecting the surface energy budget calculations and an indication of the potential effectiveness o f assimilating LST into the models.

  7. Synthesis, photophysical and electrochemical properties of a carbazole dimer-based derivative with benzothiazole units

    NASA Astrophysics Data System (ADS)

    Shi, He-ping; Dai, Jian-xin; Shi, Li-wen; Xu, Lei; Zhou, Zhao-bin; Zhang, Yan; Zhou, Wen; Dong, Chuan

    A novel A-π-D-π-D-π-A type compound, containing two benzothiazole rings as electron acceptors and two N-ethylcarbazole groups as electron donors, (E)-1,2-bis(3-(benzothiazol-2-yl)-9-ethylcarbazol-6-yl)ethene (BBECE), was synthesized and characterized by elemental analysis, NMR, MS and thermogravimetric analysis. Electrochemical property of compound BBECE was studied by cyclic voltammetry analysis. The absorption and emission spectra of BBECE was experimentally determined in several solvents and simultaneously computed using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The calculated absorption and emission wavelengths are coincident with the measured data. The lowest-lying absorption spectra can be mainly attributed to intramolecular charge transfer (ICT), and the fluorescence spectra can be mainly described as originating from an excited state with intramolecular charge transfer (ICT) character. The molecular orbitals (HOMO and LUMO), the ionization potential (IP), the electron affinity (EA) and reorganization energy of compound BBECE were also investigated using density functional theory (DFT). The results show that compound BBECE exhibited excellent thermal stability and electrochemical stability as well as high fluorescence quantum yield, indicating its potential applications as an excellent optoelectronic material in optical fields.

  8. Electrochemical polymerization of pyrene derivatives on functionalized carbon nanotubes for pseudocapacitive electrodes

    NASA Astrophysics Data System (ADS)

    Bachman, John C.; Kavian, Reza; Graham, Daniel J.; Kim, Dong Young; Noda, Suguru; Nocera, Daniel G.; Shao-Horn, Yang; Lee, Seung Woo

    2015-05-01

    Electrochemical energy-storage devices have the potential to be clean and efficient, but their current cost and performance limit their use in numerous transportation and stationary applications. Many organic molecules are abundant, economical and electrochemically active; if selected correctly and rationally designed, these organic molecules offer a promising route to expand the applications of these energy-storage devices. In this study, polycyclic aromatic hydrocarbons are introduced within a functionalized few-walled carbon nanotube matrix to develop high-energy, high-power positive electrodes for pseudocapacitor applications. The reduction potential and capacity of various polycyclic aromatic hydrocarbons are correlated with their interaction with the functionalized few-walled carbon nanotube matrix, chemical configuration and electronic structure. These findings provide rational design criteria for nanostructured organic electrodes. When combined with lithium negative electrodes, these nanostructured organic electrodes exhibit energy densities of ~350 Wh kg-1electrode at power densities of ~10 kW kg-1electrode for over 10,000 cycles.

  9. Structural, electrochemical and theoretical study of a new chalcone derivative containing 3-thiophene rings

    NASA Astrophysics Data System (ADS)

    Baggio, Ricardo; Brovelli, Francisco; Moreno, Yanko; Pinto, Marcela; Soto-Delgado, Jorge

    2016-11-01

    The title chalcone, 1,3-di(thiophene-3-yl)prop-2-en-1-one (C11H8OS2) is an essentially planar molecular with its terminal thiophene rings subtending an angle of 8.9°. The crystal structure consists in the π··π stacking of molecules defining columns along [010], further linked along c by non conventional Csbnd H⋯O bonds, thus determining broad planar arrays parallel to (100). In addition, there are weak S⋯S contacts connecting these weakly interacting 2D substructures. The experimental results obtained from single crystal X-ray diffraction data and the theoretical geometry calculated by molecular mechanics are in good agreement. Electrochemical records reveal an anodic profile with an unsymmetrical irreversible peak at 1.77 V and a shoulder at 1.62 V vs SCE, a behavior interpretable as due to the oxidation of reactive sites present in the molecule. On the other hand, the electrochemical reduction shows a narrow peak at -1.58 V vs SCE, a fact attributable to the carbonyl group. Finally, the values for the energy involved in the departure/arrival of electrons from border orbitals, as calculated using DFT, is compared with experimental data from cyclic voltammetry.

  10. Electrochemical polymerization of pyrene derivatives on functionalized carbon nanotubes for pseudocapacitive electrodes

    PubMed Central

    Bachman, John C.; Kavian, Reza; Graham, Daniel J.; Kim, Dong Young; Noda, Suguru; Nocera, Daniel G.; Shao-Horn, Yang; Lee, Seung Woo

    2015-01-01

    Electrochemical energy-storage devices have the potential to be clean and efficient, but their current cost and performance limit their use in numerous transportation and stationary applications. Many organic molecules are abundant, economical and electrochemically active; if selected correctly and rationally designed, these organic molecules offer a promising route to expand the applications of these energy-storage devices. In this study, polycyclic aromatic hydrocarbons are introduced within a functionalized few-walled carbon nanotube matrix to develop high-energy, high-power positive electrodes for pseudocapacitor applications. The reduction potential and capacity of various polycyclic aromatic hydrocarbons are correlated with their interaction with the functionalized few-walled carbon nanotube matrix, chemical configuration and electronic structure. These findings provide rational design criteria for nanostructured organic electrodes. When combined with lithium negative electrodes, these nanostructured organic electrodes exhibit energy densities of ∼350 Wh kg−1electrode at power densities of ∼10 kW kg−1electrode for over 10,000 cycles. PMID:25943905

  11. TiO2 nanostructured surfaces for biomedical applications developed by electrochemical anodization

    NASA Astrophysics Data System (ADS)

    Strnad, G.; Petrovan, C.; Russu, O.; Jakab-Farkas, L.

    2016-11-01

    Present research demonstrates the formation of self-ordered nanostructured oxide layer on the surface of two phase Ti6Al4V alloy by using electrochemical anodization in H3PO4/HF electrolytes. Our results show that the ordered oxide nanotubes grow on large areas on the samples surface, on both phases of (α+β) Ti6Al4V titanium alloy. We developed nanotubes of 70 nm (internal diameter) using 0.3 wt% HF and of 80 nm using 0.5 wt% HF additions to 1M H3PO4, at an anodization potential of 20 V, and an anodization time of 2 hours. We show that anodization potential has a strong influence on nanostructures morphology. Our results show that nanotubes’ internal diameter is ∼30 nm at 10 V potential, ∼40 nm at 15 V potential, and ∼70-80 nm at 20 V potential in anodization process performed in 1M H3PO4 + 0.5 wt% HF, 2 hours. The thickness of the developed nanostructured oxide layer is in 200-250 nm range.

  12. Sheath-flow microfluidic approach for combined surface enhanced Raman scattering and electrochemical detection.

    PubMed

    Bailey, Matthew R; Pentecost, Amber M; Selimovic, Asmira; Martin, R Scott; Schultz, Zachary D

    2015-04-21

    The combination of hydrodynamic focusing with embedded capillaries in a microfluidic device is shown to enable both surface enhanced Raman scattering (SERS) and electrochemical characterization of analytes at nanomolar concentrations in flow. The approach utilizes a versatile polystyrene device that contains an encapsulated microelectrode and fluidic tubing, which is shown to enable straightforward hydrodynamic focusing onto the electrode surface to improve detection. A polydimethyslsiloxane (PDMS) microchannel positioned over both the embedded tubing and SERS active electrode (aligned ∼200 μm from each other) generates a sheath flow that confines the analyte molecules eluting from the embedded tubing over the SERS electrode, increasing the interaction between the Riboflavin (vitamin B2) and the SERS active electrode. The microfluidic device was characterized using finite element simulations, amperometry, and Raman experiments. This device shows a SERS and amperometric detection limit near 1 and 100 nM, respectively. This combination of SERS and amperometry in a single device provides an improved method to identify and quantify electroactive analytes over either technique independently.

  13. Electrochemical DNA biosensor based on the proximity-dependent surface hybridization assay.

    PubMed

    Zhang, Yanli; Wang, Ying; Wang, Haibo; Jiang, Jian-Hui; Shen, Guo-Li; Yu, Ru-Qin; Li, Jinghong

    2009-03-01

    This paper describes a novel electrochemical DNA (E-DNA) biosensor for simple, rapid, and specific detection of nucleic acids based on the proximity-dependent surface hybridization assay. This E-DNA biosensor was constructed by self-assembly of a 3' short thiolated capture probe on the gold electrode. DNA detection was realized by outputting a remarkable redox current of the 5' ferrocene (Fc) tail labeled probe. When the target DNA was introduced into the system, it was complementary to the 5' Fc labeled probe at the one-half-segment and complementary to the 3' short thiolated capture probe at the other half-segment, resulting in forming a stable duplex complex. As a result, the Fc probe was proximate to the electrode surface, and the Faradaic current was observed. This E-DNA biosensor was proved to have a low detection limit (1 fM) and a wide dynamic range (from 1 fM to 1 nM) due to the stable hybridization mode. In addition, the sensing system could discriminate the complementary sequence from mismatch sequences, with high sensitivity, stability, and reusability.

  14. Rational Design of Bi Nanoparticles for Efficient Electrochemical CO2 Reduction: The Elucidation of Size and Surface Condition Effects

    DOE PAGES

    Zhang, Zhiyong; Chi, Miaofang; Veith, Gabriel M.; ...

    2016-08-08

    Here we report an efficient electrochemical conversion of CO2 to CO on surface-activated bismuth nanoparticles (NPs) in acetonitrile (MeCN) under ambient conditions, with the assistance of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]). Through the comparison between electrodeposited Bi films (Bi-ED) and different types of Bi NPs, we, for the first time, demonstrate the effects of catalyst’s size and surface condition on organic phase electrochemical CO2 reduction. Our study reveals that the surface inhibiting layer (hydrophobic surfactants and Bi3+ species) formed during the synthesis and purification process hinders the CO2 reduction, leading to a 20% drop in Faradaic efficiency for CO evolution (FECO). Bimore » particle size showed a significant effect on FECO when the surface of Bi was air-oxidized, but this effect of size on FECO became negligible on surface-activated Bi NPs. After the surface activation (hydrazine treatment) that effectively removed the native inhibiting layer, activated 36-nm Bi NPs exhibited an almost-quantitative conversion of CO2 to CO (96.1% FECO), and a mass activity for CO evolution (MACO) of 15.6 mA mg–1, which is three-fold higher than the conventional Bi-ED, at ₋2.0 V (vs Ag/AgCl). Ultimately, this work elucidates the importance of the surface activation for an efficient electrochemical CO2 conversion on metal NPs and paves the way for understanding the CO2 electrochemical reduction mechanism in nonaqueous media.« less

  15. Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

    NASA Astrophysics Data System (ADS)

    Sulyma, Christopher Michael

    This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu

  16. Construction of a zinc porphyrin-fullerene-derivative based nonenzymatic electrochemical sensor for sensitive sensing of hydrogen peroxide and nitrite.

    PubMed

    Wu, Hai; Fan, Suhua; Jin, Xiaoyan; Zhang, Hong; Chen, Hong; Dai, Zong; Zou, Xiaoyong

    2014-07-01

    Enzymatic sensors possess high selectivity but suffer from some limitations such as instability, complicated modified procedure, and critical environmental factors, which stimulate the development of more sensitive and stable nonenzymatic electrochemical sensors. Herein, a novel nonenzymatic electrochemical sensor is proposed based on a new zinc porphyrin-fullerene (C60) derivative (ZnP-C60), which was designed and synthesized according to the conformational calculations and the electronic structures of two typical ZnP-C60 derivatives of para-ZnP-C60 (ZnP(p)-C60) and ortho-ZnP-C60 (ZnP(o)-C60). The two derivatives were first investigated by density functional theory (DFT) and ZnP(p)-C60 with a bent conformation was verified to possess a smaller energy gap and better electron-transport ability. Then ZnP(p)-C60 was entrapped in tetraoctylammonium bromide (TOAB) film and modified on glassy carbon electrode (TOAB/ZnP(p)-C60/GCE). The TOAB/ZnP(p)-C60/GCE showed four well-defined quasi-reversible redox couples with extremely fast direct electron transfer and excellent nonenzymatic sensing ability. The electrocatalytic reduction of H2O2 showed a wide linear range from 0.035 to 3.40 mM, with a high sensitivity of 215.6 μA mM(-1) and a limit of detection (LOD) as low as 0.81 μM. The electrocatalytic oxidation of nitrite showed a linear range from 2.0 μM to 0.164 mM, with a sensitivity of 249.9 μA mM(-1) and a LOD down to 1.44 μM. Moreover, the TOAB/ZnP(p)-C60/GCE showed excellent stability and reproducibility, and good testing recoveries for analysis of the nitrite levels of river water and rainwater. The ZnP(p)-C60 can be used as a novel material for the fabrication of nonenzymatic electrochemical sensors.

  17. Inherently-Forced Tensile Strain in Nanodiamond-Derived Onion-like Carbon: Consequences in Defect-Induced Electrochemical Activation

    PubMed Central

    Ko, Young-Jin; Cho, Jung-Min; Kim, Inho; Jeong, Doo Seok; Lee, Kyeong-Seok; Park, Jong-Keuk; Baik, Young-Joon; Choi, Heon-Jin; Lee, Seung-Cheol; Lee, Wook-Seong

    2016-01-01

    We analyzed the nanodiamond-derived onion-like carbon (OLC) as function of synthesis temperature (1000~1400 °C), by high-resolution electron microscopy, electron energy loss spectroscopy, visible-Raman spectroscopy, ultraviolet photoemission spectroscopy, impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. The temperature dependences of the obtained properties (averaged particle size, tensile strain, defect density, density of states, electron transfer kinetics, and electrochemical oxidation current) unanimously coincided: they initially increased and saturated at 1200 °C. It was attributed to the inherent tensile strains arising from (1) the volume expansion associated with the layer-wise diamond-to-graphite transformation of the core, which caused forced dilation of the outer shells during their thermal synthesis; (2) the extreme curvature of the shells. The former origin was dominant over the latter at the outermost shell, of which the relevant evolution in defect density, DOS and electron transfer kinetics determined the electrochemical performances. In detection of dopamine (DA), uric acid (UA) and ascorbic acid (AA) using the OLC as electrode, their oxidation peak currents were enhanced by factors of 15~60 with annealing temperature. Their limit of detection and the linear range of detection, in the post-treatment-free condition, were as excellent as those of the nano-carbon electrodes post-treated by Pt-decoration, N-doping, plasma, or polymer. PMID:27032957

  18. Inherently-Forced Tensile Strain in Nanodiamond-Derived Onion-like Carbon: Consequences in Defect-Induced Electrochemical Activation

    NASA Astrophysics Data System (ADS)

    Ko, Young-Jin; Cho, Jung-Min; Kim, Inho; Jeong, Doo Seok; Lee, Kyeong-Seok; Park, Jong-Keuk; Baik, Young-Joon; Choi, Heon-Jin; Lee, Seung-Cheol; Lee, Wook-Seong

    2016-04-01

    We analyzed the nanodiamond-derived onion-like carbon (OLC) as function of synthesis temperature (1000~1400 °C), by high-resolution electron microscopy, electron energy loss spectroscopy, visible-Raman spectroscopy, ultraviolet photoemission spectroscopy, impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. The temperature dependences of the obtained properties (averaged particle size, tensile strain, defect density, density of states, electron transfer kinetics, and electrochemical oxidation current) unanimously coincided: they initially increased and saturated at 1200 °C. It was attributed to the inherent tensile strains arising from (1) the volume expansion associated with the layer-wise diamond-to-graphite transformation of the core, which caused forced dilation of the outer shells during their thermal synthesis; (2) the extreme curvature of the shells. The former origin was dominant over the latter at the outermost shell, of which the relevant evolution in defect density, DOS and electron transfer kinetics determined the electrochemical performances. In detection of dopamine (DA), uric acid (UA) and ascorbic acid (AA) using the OLC as electrode, their oxidation peak currents were enhanced by factors of 15~60 with annealing temperature. Their limit of detection and the linear range of detection, in the post-treatment-free condition, were as excellent as those of the nano-carbon electrodes post-treated by Pt-decoration, N-doping, plasma, or polymer.

  19. Electrochemical characterization of thio sol-gel derived titanium sulfide (TiS{sub 2}) powders with unique morphologies

    SciTech Connect

    Sriram, M.A.; Kumta, P.N.

    1996-12-31

    A novel thio sol-gel process utilizing titanium alkoxide as the metal source has been used to synthesize TiS{sub 2} powders exhibiting uniquely different morphologies. The pure alkoxide and its partially modified form using benzene sulfonic acid (BSA) have been reacted with H{sub 2}S to yield a solid precursor. Upon heat treatment in flowing H{sub 2}S the precursors were converted to TiS{sub 2} exhibiting distinctly different morphologies. These powders have been characterized for their chemical stoichiometry (using X-ray diffraction). At the same time the sulfide was also prepared using conventional techniques involving the reaction of the individual elements in a sealed evacuated quartz ampoule at elevated temperatures of 500{degrees}C. The morphologies of both, the thio sol-gel derived and conventionally synthesized powders have been compared using scanning electron microscopy (SEM). Preliminary electrochemical tests were also performed by fabricating test cathodes of these materials and using them in {open_quotes}hockey puck{close_quotes} cells incorporating lithium as both the anode and the reference electrodes. These studies were conducted to analyze the effect of the different morphologies of the synthesized powders on their electrochemical performance.

  20. Comparison of Morphology, Orientation, and Migration of Tendon Derived Fibroblasts and Bone Marrow Stromal Cells on Electrochemically Aligned Collagen Constructs

    PubMed Central

    Gurkan, Umut Atakan; Cheng, Xingguo; Kishore, Vipuil; Uquillas, Jorge Alfredo; Akkus, Ozan

    2010-01-01

    There are approximately 33 million injuries involving musculoskeletal tissues (including tendons and ligaments) every year in the United States. In certain cases the tendons and ligaments are damaged irreversibly and require replacements that possess the natural functional properties of these tissues. As a biomaterial, collagen has been a key ingredient in tissue engineering scaffolds. The application range of collagen in tissue engineering would be greatly broadened if the assembly process could be better controlled to facilitate the synthesis of dense, oriented tissue-like constructs. An electrochemical method has recently been developed in our laboratory to form highly oriented and densely packed collagen bundles with mechanical strength approaching that of tendons. However, there is limited information whether this electrochemically aligned collagen bundle (ELAC) presents advantages over randomly oriented bundles in terms of cell response. Therefore, the current study aimed to assess the biocompatibility of the collagen bundles in vitro, and compare tendon derived fibroblasts (TDFs) and bone marrow stromal cells (MSCs) in terms of their ability to populate and migrate on the single and braided ELAC bundles. The results indicated that the ELAC was not cytotoxic; both cell types were able to populate and migrate on the ELAC bundles more efficiently than that observed for random collagen bundles. The braided ELAC constructs were efficiently populated by both TDFs and MSCs in vitro. Therefore, both TDFs and MSCs can be used with the ELAC bundles for tissue engineering purposes. PMID:20694974

  1. Electrochemical and surface plasmon resonance characterization of β-cyclodextrin-based self-assembled monolayers and evaluation of their inclusion complexes with glucocorticoids

    NASA Astrophysics Data System (ADS)

    Frasconi, Marco; Mazzei, Franco

    2009-07-01

    This paper describes the characterization of a self-assembled β-cyclodextrin (β-CD)-derivative monolayer (β-CD-SAM) on a gold surface and the study of their inclusion complexes with glucocorticoids. To this aim the arrangement of a self-assembled β-cyclodextrin-derivative monolayer on a gold surface was monitored in situ by means of surface plasmon resonance (SPR) spectroscopy and double-layer capacitance measurements. Film thickness and dielectric constant were evaluated for a monolayer of β-CD using one-color-approach SPR. The selectivity of the β-CD host surface was verified by using electroactive species permeable and impermeable in the β-CD cavity. The redox probe was selected according to its capacity to permeate the β-CD monolayer and its electrochemical behavior. In order to evaluate the feasibility of an inclusion complex between β-CD-SAM with some steroids such as cortisol and cortisone, voltammetric experiments in the presence of the redox probes as molecules competitive with the steroids have been performed. The formation constant of the surface host-guest by β-CD-SAM and the steroids under study was calculated.

  2. Anisotropic surface hole-transport property of triphenylamine-derivative single crystal prepared by solution method

    NASA Astrophysics Data System (ADS)

    Umeda, Minoru; Katagiri, Mitsuhiko; Shironita, Sayoko; Nagayama, Norio

    2016-12-01

    This paper reports the anisotropic hole transport at the triphenylamine-derivative single crystal surface prepared by a solution method. Triphenylamine derivatives are commonly used in a hole-transport material for organic photoconductors of laser-beam printers, in which the materials are used as an amorphous form. For developing organic photovoltaics using the photoconductor's technology, preparation of a single crystal seems to be a specific way by realizing the high mobility of an organic semiconductor. In this study, a single crystal of 4-(2,2-diphenylethenyl)-N,N-bis(4-methylphenyl)-benzenamine (TPA) was prepared and its anisotropic hole-transport property measured. First, the hole-transport property of the TPA was investigated based on its chemical structure and electrochemical redox characteristics. Next, a large-scale single crystal formation at a high rate was developed by employing a solution method based on its solubility and supersolubility curves. The grown TPA was found to be a single crystal based on the polarization micrograph observation and crystallographic analysis. For the TPA single crystal, an anisotropic surface conduction was found, which was well explained by its molecular stack structure. The measured current in the long-axis direction is one order of magnitude greater than that of amorphous TPA.

  3. Molecular encapsulation of 5-nitroindazole derivatives in 2,6-dimethyl-beta-cyclodextrin: electrochemical and spectroscopic studies.

    PubMed

    Pérez-Cruz, Fernanda; Jullian, Carolina; Rodriguez, Jorge; Arán, Vicente J; Olea-Azar, Claudio

    2009-07-01

    Four different 5-nitroindazole derivatives (1-4) and its inclusion with Heptakis(2,6-di-O-methyl)-beta-cyclodextrin (DMbetaCD) were investigated. The stoichiometric ratios and stability constants describing the extent of formation of the complexes were determined by phase-solubility measurements obtaining in all cases a type-A(L) diagram. Also electrochemical studies were carried out, where the observed change in the E(PC) value indicated a lower feasibility of the nitro group reduction. The same behavior was observed in the ESR studies. The detailed spatial configuration is proposed based on 2D NMR methods. These results are further interpreted using molecular modeling studies. The latter results are in good agreement with the experimental data.

  4. Effect of surface derived hydrocarbon impurities on Ar plasma properties

    SciTech Connect

    Fox-Lyon, Nick; Oehrlein, Gottlieb S.; Godyak, Valery

    2014-05-15

    The authors report on Langmuir probe measurements that show that hydrocarbon surfaces in contact with Ar plasma cause changes of electron energy distribution functions due to the flux of hydrogen and carbon atoms released by the surfaces. The authors compare the impact on plasma properties of hydrocarbon species gasified from an etching hydrocarbon surface with injection of gaseous hydrocarbons into Ar plasma. They find that both kinds of hydrocarbon injections decrease electron density and slightly increase electron temperatures of low pressure Ar plasma. For low percentages of impurities (∼1% impurity in Ar plasma explored here), surface-derived hydrocarbon species and gas phase injected hydrocarbon molecules cause similar changes of plasma properties for the same number of hydrocarbon molecules injected into Ar with a decrease in electron density of ∼4%.

  5. Surface Modification Approach to TiO2 Nanofluids with High Particle Concentration, Low Viscosity, and Electrochemical Activity.

    PubMed

    Sen, Sujat; Govindarajan, Vijay; Pelliccione, Christopher J; Wang, Jie; Miller, Dean J; Timofeeva, Elena V

    2015-09-23

    This study presents a new approach to the formulation of functional nanofluids with high solid loading and low viscosity while retaining the surface activity of nanoparticles, in particular, their electrochemical response. The proposed methodology can be applied to a variety of functional nanomaterials and enables exploration of nanofluids as a medium for industrial applications beyond heat transfer fluids, taking advantage of both liquid behavior and functionality of dispersed nanoparticles. The highest particle concentration achievable with pristine 25 nm titania (TiO2) nanoparticles in aqueous electrolytes (pH 11) is 20 wt %, which is limited by particle aggregation and high viscosity. We have developed a scalable one-step surface modification procedure for functionalizing those TiO2 nanoparticles with a monolayer coverage of propyl sulfonate groups, which provides steric and charge-based separation of particles in suspension. Stable nanofluids with TiO2 loadings up to 50 wt % and low viscosity are successfully prepared from surface-modified TiO2 nanoparticles in the same electrolytes. Viscosity and thermal conductivity of the resulting nanofluids are evaluated and compared to nanofluids prepared from pristine nanoparticles. Furthermore, it is demonstrated that the surface-modified titania nanoparticles retain more than 78% of their electrochemical response as compared to that of the pristine material. Potential applications of the proposed nanofluids include, but are not limited to, electrochemical energy storage and catalysis, including photo- and electrocatalysis.

  6. Molecular switches from benzene derivatives adsorbed on metal surfaces

    PubMed Central

    Liu, Wei; Filimonov, Sergey N.; Carrasco, Javier; Tkatchenko, Alexandre

    2013-01-01

    Transient precursor states are often experimentally observed for molecules adsorbing on surfaces. However, such precursor states are typically rather short-lived, quickly yielding to more stable adsorption configurations. Here we employ first-principles calculations to systematically explore the interaction mechanism for benzene derivatives on metal surfaces, enabling us to selectively tune the stability and the barrier between two metastable adsorption states. In particular, in the case of the tetrachloropyrazine molecule, two equally stable adsorption states are identified with a moderate and conceivably reversible barrier between them. We address the feasibility of experimentally detecting the predicted bistable behaviour and discuss its potential usefulness in a molecular switch. PMID:24157660

  7. Surface analysis, microstructural, mechanical and electrochemical properties of new Ti-15Ta-5Zr alloy

    NASA Astrophysics Data System (ADS)

    Vasilescu, Cora; Drob, Silviu Iulian; Osiceanu, Petre; Drob, Paula; Moreno, Jose Maria Calderon; Preda, Silviu; Ivanescu, Steliana; Vasilescu, Ecaterina

    2015-03-01

    This paper describes the synthesis of a novel Ti-15Ta-5Zr alloy with an α + ß stable, homogeneous, biphasic microstructure (by optical microscopy, X-ray diffraction and scanning electron microscopy) and the determination of its mechanical properties, hardness and a Young's modulus of 42.2 GPa. The alloy passive film composition and thickness were analyzed by X-ray photoelectron spectroscopy; a thick, compact native passive film containing the protective oxides of all constituent elements (TiO2, Ta2O5, ZrO2) was identified. The electrochemical parameters confirmed a nobler behaviour and a more capacitive, resistant passive film on the alloy surface compared to Ti and other existing implant alloys; these facts are due to the alloying elements that, by their oxides stabilize and reinforce the alloy passive film. This passive film thickened in time, which increased its protective capacity. The new alloy had no susceptibility to galvanic or local corrosion. Ti-15Ta-5Zr alloy is recommended as an advanced orthopaedic implant material.

  8. Electrochemically prepared surface-enhanced Raman scattering-active silver substrates with improved stabilities

    NASA Astrophysics Data System (ADS)

    Yang, Kuang-Hsuan; Liu, Yu-Chuan; Yu, Chung-Chin; Chen, Bo-Chuen

    2011-01-01

    In this work, SiO 2 nanoparticles-modified surface-enhanced Raman scattering (SERS)-active silver substrates were prepared by electrochemical oxidation-reduction cycles (ORC) methods in 0.1 N HCl aqueous solutions containing 1 mM SiO 2 nanoparticles to improve their thermal stabilities and anti-aging abilities in SERS performances. Then these SERS-active substrates were further modified with different contents of SiO 2 nanoparticles to improve their corresponding SERS performances. Experimental results indicate that the operation temperature can be significantly raised from 125 to 175 °C based on this modified SERS-active Ag substrate. Also, the aging in SERS intensity is also depressed on this modified Ag substrate due to the contribution of SiO 2 nanoparticles. Moreover, the SERS enhancement capability on this modified Ag substrate is gradually raised from 25 °C to a maximum at 55 °C and monotonically decreased from 55 to 60 °C. This is a 10 °C delay as compared with the similar phenomenon observed on the unmodified Ag substrate.

  9. Nano-Ag-loaded hydroxyapatite coatings on titanium surfaces by electrochemical deposition.

    PubMed

    Lu, Xiong; Zhang, Bailin; Wang, Yingbo; Zhou, Xianli; Weng, Jie; Qu, Shuxin; Feng, Bo; Watari, Fumio; Ding, Yonghui; Leng, Yang

    2011-04-06

    Hydroxyapatite (HA) coatings on titanium (Ti) substrates have attracted much attention owing to the combination of good mechanical properties of Ti and superior biocompatibility of HA. Incorporating silver (Ag) into HA coatings is an effective method to impart the coatings with antibacterial properties. However, the uniform distribution of Ag is still a challenge and Ag particles in the coatings are easy to agglomerate, which in turn affects the applications of the coatings. In this study, we employed pulsed electrochemical deposition to co-deposit HA and Ag simultaneously, which realized the uniform distribution of Ag particles in the coatings. This method was based on the use of a well-designed electrolyte containing Ag ions, calcium ions and l-cysteine, in which cysteine acted as the coordination agent to stabilize Ag ions. The antibacterial and cell culture tests were used to evaluate the antibacterial properties and biocompatibility of HA/Ag composite coatings, respectively. The results indicated the as-prepared coatings had good antibacterial properties and biocompatibility. However, an appropriate silver content should be chosen to balance the biocompatibility and antibacterial properties. Heat treatments promoted the adhesive strength and enhanced the biocompatibility without sacrificing the antibacterial properties of the HA/Ag coatings. In summary, this study provided an alternative method to prepare bioactive surfaces with bactericidal ability for biomedical devices.

  10. Surface and Electrochemical Behavior of HSLA in Supercritical CO2-H2O Environment

    SciTech Connect

    M. Ziomek-Moroz; G. R. Holcomb; J. Tylczak; J. Beck; M. Fedkin; S. Lvov

    2012-01-11

    General corrosion was observed on high strength low alloy carbon steel after electrochemical impedance spectroscopy experiments (EIS) performed in H{sub 2}O saturated with CO{sub 2} at 50 C and 15.2 MPa. However, general and localized were observed on the same material surfaces after the EIS experiments performed in supercritical CO{sub 2} containing approximately 6100 ppmv H{sub 2}O at 50 C and 15.2 MPa. The general corrosion areas were uniformly covered by the FeCO{sub 3}-like phase identified by X-ray diffraction (XRD). In the area of localized corrosion, XRD also revealed FeCO{sub 3}-rich islands embedded in {alpha}-iron. The energy dispersive X-ray (EDX) analysis revealed high concentrations of iron, carbon, and oxygen in the area affected by general corrosion and in the islands formed in the area of localized corrosion. The real and imaginary impedances were lower in H{sub 2}O saturated with CO{sub 2} than those in the supercritical CO{sub 2} containing the aqueous phase indicating faster corrosion kinetics in the former.

  11. Off surface matrix based on-chip electrochemical biosensor platform for protein biomarker detection in undiluted serum.

    PubMed

    Arya, Sunil K; Kongsuphol, Patthara; Park, Mi Kyoung

    2017-06-15

    The manuscript describes a concept of using off surface matrix modified with capturing biomolecule for on-chip electrochemical biosensing. 3D matrix made by laser engraving of polymethyl methacrylate (PMMA) sheet as off surface matrix was integrated in very close vicinity of the electrode surface. Laser engraving and holes in PMMA along with spacing from surface provide fluidic channel and incubation chamber. Covalent binding of capturing biomolecule (anti-TNF-α antibody) on off-surface matrix was achieved via azide group activity of 4-fluoro-3-nitro-azidobenzene (FNAB), which act as cross-linker and further covalently binds to anti-TNF-α antibody via thermal reaction. Anti-TNF-α/FNAB/PMMA matrix was then integrated over comb structured gold electrode array based sensor chip. Separate surface modification followed by integration of sensor helped to prevent the sensor chip surface from fouling during functionalization. Nonspecific binding was prevented using starting block T20 (PBS). Results for estimating protein biomarker (TNF-α) in undiluted serum using Anti-TNF-α/FNAB/PMMA/Au reveal that system can detect TNF-α in 100pg/ml to 100ng/ml range with high sensitivity of 119nA/(ng/ml), with negligible interference from serum proteins and other cytokines. Thus, use of off surface matrix may provide the opportunity to electrochemically sense biomarkers sensitively to ng/ml range with negligible nonspecific binding and false signal in undiluted serum.

  12. Electrochemical surface modification of carbon mesh anode to improve the performance of air-cathode microbial fuel cells.

    PubMed

    Luo, Jianmei; Chi, Meiling; Wang, Hongyu; He, Huanhuan; Zhou, Minghua

    2013-12-01

    A convenient and promising alternative to surface modification of carbon mesh anode was fulfilled by electrochemical oxidation in the electrolyte of nitric acid or ammonium nitrate at ambient temperature. It was confirmed that such an anode modification method was low cost and effective not only in improving the efficiency of power generation in microbial fuel cells (MFCs) for synthetic wastewater treatment, but also helping to reduce the period for MFCs start-up. The MFCs with anode modification in electrolyte of nitric acid performed the best, achieving a Coulombic efficiency enhancement of 71 %. As characterized, the electrochemical modification resulted in the decrease of the anode potential and internal resistance but the increase of current response and nitrogen-containing and oxygen-containing functional groups on the carbon surface, which might contribute to the enhancement on the performances of MFCs.

  13. Theoretical approach for optical response in electrochemical systems: Application to electrode potential dependence of surface-enhanced Raman scattering

    SciTech Connect

    Iida, Kenji; Noda, Masashi; Nobusada, Katsuyuki

    2014-09-28

    We propose a theoretical approach for optical response in electrochemical systems. The fundamental equation to be solved is based on a time-dependent density functional theory in real-time and real-space in combination with its finite temperature formula treating an electrode potential. Solvation effects are evaluated by a dielectric continuum theory. The approach allows us to treat optical response in electrochemical systems at the atomistic level of theory. We have applied the method to surface-enhanced Raman scattering (SERS) of 4-mercaptopyridine on an Ag electrode surface. It is shown that the SERS intensity has a peak as a function of the electrode potential. Furthermore, the real-space computational approach facilitates visualization of variation of the SERS intensity depending on an electrode potential.

  14. Energy storage on ultrahigh surface area activated carbon fibers derived from PMIA.

    PubMed

    Castro-Muñiz, Alberto; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M D; Kyotani, Takashi

    2013-08-01

    High-performance carbon materials for energy storage applications have been obtained by using poly(m-phenylene isophthalamide), PMIA, as a precursor through the chemical activation of the carbonized aramid fiber by using KOH. The yield of the process of activation was remarkably high (25-40 wt%), resulting in activated carbon fibers (ACFs) with ultrahigh surface areas, over 3000 m(2) g(-1) , and pore volumes exceeding 1.50 cm(3) g(-1) , keeping intact the fibrous morphology. The porous structure and the surface chemical properties could easily be controlled through the conditions of activation. The PMIA-derived ACFs were tested in two types of energy storage applications. At -196 °C and 1 bar, H2 uptake values of approximately 3 t% were obtained, which, in combination with the textural properties, rendered it a good candidate for H2 adsorption at high pressure and temperature. The performance of the ACFs as electrodes for electrochemical supercapacitors was also investigated. Specific capacitance values between 297 and 531 g(-1) at 50 mA g(-1) were obtained in aqueous electrolyte (1 H2 SO4 ), showing different behaviors depending on the surface chemical properties.

  15. Renewable Solid Electrodes in Microfluidics: Recovering the Electrochemical Activity without Treating the Surface.

    PubMed

    Teixeira, Carlos A; Giordano, Gabriela F; Beltrame, Maisa B; Vieira, Luis C S; Gobbi, Angelo L; Lima, Renato S

    2016-11-15

    The contamination, passivation, or fouling of the detection electrodes is a serious problem undermining the analytical performance of electroanalytical devices. The methods to regenerate the electrochemical activity of the solid electrodes involve mechanical, physical, or chemical surface treatments that usually add operational time, complexity, chemicals, and further instrumental requirements to the analysis. In this paper, we describe for the first time a reproducible method for renewing solid electrodes whenever their morphology or composition are nonspecifically changed without any surface treatment. These renewable electrodes are the closest analogue to the mercury drop electrodes. Our approach was applied in microfluidics, where the downsides related to nonspecific modifications of the electrode are more critical. The renewal consisted in manually sliding metal-coated microwires across a channel with the sample. For this purpose, the chip was composed of a single piece of polydimethylsiloxane (PDMS) with three parallel channels interconnected to one perpendicular and top channel. The microwires were inserted in each one of the parallel channels acting as working, counter, and pseudoreference electrodes for voltammetry. This assembly allowed the renewal of all the three electrodes by simply pulling the microwires. The absence of any interfaces in the chips and the elastomeric nature of the PDMS allowed us to pull the microwires without the occurrence of leakages for the electrode channels even at harsh flow rates of up to 40.0 mL min(-1). We expect this paper can assist the researchers to develop new microfluidic platforms that eliminate any steps of electrode cleaning, representing a powerful alternative for precise and robust analyses to real samples.

  16. Superhydrophilic graphite surfaces and water-dispersible graphite colloids by electrochemical exfoliation

    SciTech Connect

    Li, Yueh-Feng; Chen, Shih-Ming; Lai, Wei-Hao; Sheng, Yu-Jane; Tsao, Heng-Kwong

    2013-08-14

    Superhydrophilic graphite surfaces and water-dispersible graphite colloids are obtained by electrochemical exfoliation with hydrophobic graphite electrodes. Such counterintuitive characteristics are caused by partial oxidation and investigated by examining both graphite electrodes and exfoliated particles after electrolysis. The extent of surface oxidation can be explored through contact angle measurement, scanning electron microscope, electrical sheet resistance, x-ray photoelectron spectroscopy, zeta-potential analyzer, thermogravimetric analysis, UV-visible, and Raman spectroscopy. The degree of wettability of the graphite anode can be altered by the electrolytic current and time. The water contact angle declines generally with increasing the electrolytic current or time. After a sufficient time, the graphite anode becomes superhydrophilic and its hydrophobicity can be recovered by peeling with adhesive tape. This consequence reveals that the anodic graphite is oxidized by oxygen bubbles but the oxidation just occurs at the outer layers of the graphite sheet. Moreover, the characteristics of oxidation revealed by UV peak shift, peak ratio between D and G bands, and negative zeta-potential indicate the presence of graphite oxide on the outer shell of the exfoliated colloids. However, thermogravimetric analysis for the extent of decomposition of oxygen functional groups verifies that the amount of oxygen groups is significantly less than that of graphite oxide prepared via Hummer method. The structure of this partially oxidized graphite may consist of a graphite core covered with an oxidized shell. The properties of the exfoliated colloids are also influenced by pH of the electrolytic solution. As pH is increased, the extent of oxidation descends and the thickness of oxidized shell decreases. Those results reveal that the degree of oxidation of exfoliated nanoparticles can be manipulated simply by controlling pH.

  17. Anticancer, photoluminescence and electrochemical properties of structurally characterized two imine derivatives.

    PubMed

    Ceyhan, Gökhan; Köse, Muhammet; Tümer, Mehmet; Demirtaş, İbrahim

    2015-01-01

    Two imine compounds, 4-[(E)-(2-methoxybenzylidene)amino]phenol (L(1)) and 4-[(E)-(3,4-dimethoxybenzylidene)amino]phenol (L(2)) were synthesized and characterized by the analytical and spectroscopic methods. The electrochemical and photoluminescence properties of the imine compounds L(1) and L(2) were investigated in different solvents. The compounds L(1) and L(2) show different redox processes at some potentials. The molecular structures of two Schiff base compounds are broadly similar, differing principally in the position, the number of methoxy (-OCH3) groups and dihedral angles between aromatic rings. While the compound L(1) has only one methoxy group located on the o-position with respect to the imine bond (C=N), the L(2) contains two methoxy groups on the p-m-positions with respect to the imine bond. The imine compounds show two or three emission bands in the 619-832 nm range in organic solvents. In the 1.0×10(-3) M concentration, the compounds have the highest excitation and emission bands. The imine compounds L(1) and L(2) were screened for their in vitro cytotoxicity on HeLa cell lines using the xCELLigence system (Real Time Cell Analyzer).

  18. Electrochemical Urea Biosensor Based on Sol-gel Derived Nanostructured Cerium Oxide

    NASA Astrophysics Data System (ADS)

    Ansari, Anees A.; Azahar, Md; Malhotra, B. D.

    2012-04-01

    Urease (Urs) and glutamate dehydrogenase (GLDH) have been co-immobilized onto a nanostructured-cerium oxide (Nano-CeO2) film deposited onto a indium-tin-oxide (ITO) coated glass substrate by dip-coating via sol-gel process for urea detection. This nanostructured film has characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR), Scanning electron microscope (SEM) and electrochemical techniques, respectively. The particle size of the Nano-CeO2 film has been found to be 23 nm. Electrochemcial response (CV) studies show that Ur-GLDH/Nano-CeO2/ITO bioelectrode is found to be sensitive in the 10-80 mg/dL urea concentration range and can detect urea concentration upto 0.1 mg/dL level. The value of Michaelis-Menten constant (Km) estimated using Lineweaver-Burke plot found as 6.09 mg/dL indicates enhancement in the affinity and/or activity of enzyme attached to their nanobiocomposite. This bioelectrode retained 95% of enzyme activity after 6 months at 4°C.

  19. Electrochemical nanocomposite-derived sensor for the analysis of chemical oxygen demand in urban wastewaters.

    PubMed

    Gutiérrez-Capitán, Manuel; Baldi, Antoni; Gómez, Raquel; García, Virginia; Jiménez-Jorquera, Cecilia; Fernández-Sánchez, César

    2015-02-17

    This work reports on the fabrication and comparative analytical assessment of electrochemical sensors applied to the rapid analysis of chemical oxygen demand (COD) in urban waste waters. These devices incorporate a carbon nanotube-polystyrene composite, containing different inorganic electrocatalysts, namely, Ni, NiCu alloy, CoO, and CuO/AgO nanoparticles. The sensor responses were initially evaluated using glucose as standard analyte and then by analyzing a set of real samples from urban wastewater treatment plants. The estimated COD values in the samples were compared with those provided by an accredited laboratory using the standard dichromate method. The sensor prepared with the CuO/AgO-based nanocomposite showed the best analytical performance. The recorded COD values of both the sensor and the standard method were overlapped, considering the 95% confidence intervals. In order to show the feasible application of this approach for the detection of COD online and in continuous mode, the CuO/AgO-based nanocomposite sensor was integrated in a compact flow system and applied to the detection of wastewater samples, showing again a good agreement with the values provided by the dichromate method.

  20. Electrochemical Surface Potential due to Classical Point Charge Models Drives Anion Adsorption to the Air-Water Interface

    SciTech Connect

    Baer, Marcel D.; Stern, Abraham C.; Levin, Yan; Tobias, Douglas J.; Mundy, Christopher J.

    2012-06-07

    Herein, we present research that suggests that the underlying physics that drive simple empirical models of anions (e.g. point charge, no polarization) to the air-water interface, with water described by SPC/E, or related partial charge models is different than when both ions and water are modeled with quantum mechanical based interactions. Specifically, we will show that the driving force of ions to the air-water interface for point charge models results from both cavitation and the negative electrochemical surface potential. We will demonstrate that we can fully characterize the role of the free energy due to the electrochemical surface potential computed from simple empirical models and its role in ionic adsorption within the context of dielectric continuum theory (DCT). Our research suggests that a significant part of the electrochemical surface potential in empirical models appears to be an artifact of the failure of point charge models in the vicinity of a broken symmetry. This work was supported by the U.S. Department of Energy‘s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the Department of Energy by Battelle.

  1. Membrane surface functionalization via theophylline derivative coating and streptavidin immobilization.

    PubMed

    Hierrezuelo, J; Romero, V; Benavente, J; Rico, R; López-Romero, J Manuel

    2014-01-01

    Poly(vinylidene fluoride) (PVDF) and regenerated cellulose (RC) membranes were surface-modified by the adsorption of one adenosine receptor antagonist: the theophylline-oligo(ethylene glycol)-alkene derivative, Theo1. Surface modification was carried out by immersion of the membrane in a dichloromethane solution of Theo1 (PVDF+Theo1 and RC+Theo1 samples). Membrane surfaces with partial coverage by theophylline and/or its inclusion in the membrane structures were studied by X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (SNMR), impedance spectroscopy (IS) and contact angle (CA) measurements. The Theo1 orientation was inferred from the data. Streptavidin (SA) was immobilized onto the membrane/Theo1 hybrid material. The protein-theophylline Theo1 interaction was visualized with bright field microscopy (BFM).

  2. Electrochemical hydrogenation of a homogeneous nickel complex to form a surface adsorbed hydrogen-evolving species.

    PubMed

    Martin, Daniel J; McCarthy, Brian D; Donley, Carrie L; Dempsey, Jillian L

    2015-03-28

    A Ni(II) complex degrades electrochemically in the presence of acid in acetonitrile to form an electrode adsorbed film that catalytically evolves hydrogen. Comparison with a similar compound permitted investigation of the degradation mechanism.

  3. Simulation of the stationary electrochemical surface treatment by two asymmetric cathode plates

    NASA Astrophysics Data System (ADS)

    Klokov, V. V.; Sergeev, D. E.

    2012-11-01

    The hydrodynamic analogy method was used to solve the problem of stationary electrochemical shaping with two semi-infinite cathode plates arranged arbitrarily relative to the feed direction. A feature of the problem is the multivalence of the velocity hodograph.

  4. A Mass Spectrometric-Derived Cell Surface Protein Atlas

    PubMed Central

    Bausch-Fluck, Damaris; Hofmann, Andreas; Bock, Thomas; Frei, Andreas P.; Cerciello, Ferdinando; Jacobs, Andrea; Moest, Hansjoerg; Omasits, Ulrich; Gundry, Rebekah L.; Yoon, Charles; Schiess, Ralph; Schmidt, Alexander; Mirkowska, Paulina; Härtlová, Anetta; Van Eyk, Jennifer E.; Bourquin, Jean-Pierre; Aebersold, Ruedi; Boheler, Kenneth R.; Zandstra, Peter; Wollscheid, Bernd

    2015-01-01

    Cell surface proteins are major targets of biomedical research due to their utility as cellular markers and their extracellular accessibility for pharmacological intervention. However, information about the cell surface protein repertoire (the surfaceome) of individual cells is only sparsely available. Here, we applied the Cell Surface Capture (CSC) technology to 41 human and 31 mouse cell types to generate a mass-spectrometry derived Cell Surface Protein Atlas (CSPA) providing cellular surfaceome snapshots at high resolution. The CSPA is presented in form of an easy-to-navigate interactive database, a downloadable data matrix and with tools for targeted surfaceome rediscovery (http://wlab.ethz.ch/cspa). The cellular surfaceome snapshots of different cell types, including cancer cells, resulted in a combined dataset of 1492 human and 1296 mouse cell surface glycoproteins, providing experimental evidence for their cell surface expression on different cell types, including 136 G-protein coupled receptors and 75 membrane receptor tyrosine-protein kinases. Integrated analysis of the CSPA reveals that the concerted biological function of individual cell types is mainly guided by quantitative rather than qualitative surfaceome differences. The CSPA will be useful for the evaluation of drug targets, for the improved classification of cell types and for a better understanding of the surfaceome and its concerted biological functions in complex signaling microenvironments. PMID:25894527

  5. Effect of electrochemical treatment in H2SO4 aqueous solution on carbon material derived from cellulose with added guanidine phosphate

    NASA Astrophysics Data System (ADS)

    Tsubota, Toshiki; Wang, Chuanshu; Murakami, Naoya; Ohno, Teruhisa

    2013-03-01

    The electrochemical treatment in a 1 M H2SO4 aqueous solution is applied to the carbon material synthesized from cellulose mixed with guanidine phosphate. The capacitance value increased by the addition of guanidine phosphate; furthermore, the value significantly increased by the electrochemical treatment and was higher than 350 F g-1 at 50 mA g-1. The process used in this study, that is, removing the lignin from wood waste products, such as bamboo, and then mixing with guanidine phosphate before the heat treatment followed by an electrochemical treatment, should be of benefit for the synthesis of a high performance material for the electrodes of electrochemical capacitors. The significant enhancement of the capacitance value appears in the range of 1.5 V∼2.8 V vs. Ag/AgCl for the applied maximum voltage. This voltage range is consistent with the voltage for the significant enhancement of the current value in the CV curve. The change in the capacitance value should be related to the electrochemical reaction of the water electrolysis. The XPS data indicated that the concentrations of both the N atom and the O atom on the surface increased after the electrochemical process.

  6. Electrochemical Behavior of Disposable Electrodes Prepared by Ion Beam Based Surface Modification for Biomolecular Recognition

    SciTech Connect

    Erdem, A.; Karadeniz, H.; Caliskan, A.; Urkac, E. Sokullu; Oztarhan, A.; Oks, E.; Nikolayev, A.

    2009-03-10

    Many important technological advances have been made in the development of technologies to monitor interactions and recognition events of biomolecules in solution and on solid substrates. The development of advanced biosensors could impact significantly the areas of genomics, proteomics, biomedical diagnostics and drug discovery. In the literature, there have recently appeared an impressive number of intensive designs for electrochemical monitoring of biomolecular recognition. Herein, the influence of ion implanted disposable graphite electrodes on biomolecular recognition and their electrochemical behaviour was investigated.

  7. Electrochemical Coupling of Biomass-Derived Acids: New C8 Platforms for Renewable Polymers and Fuels.

    PubMed

    Wu, Linglin; Mascal, Mark; Farmer, Thomas J; Arnaud, Sacha Pérocheau; Wong Chang, Maria-Angelica

    2017-01-10

    Electrolysis of biomass-derived carbonyl compounds is an alternative to condensation chemistry for supplying products with chain length >C6 for biofuels and renewable materials production. Kolbe coupling of biomass-derived levulinic acid is used to obtain 2,7-octanedione, a new platform molecule only two low process-intensity steps removed from raw biomass. Hydrogenation to 2,7-octanediol provides a chiral secondary diol largely unknown to polymer chemistry, whereas intramolecular aldol condensation followed by hydrogenation yields branched cycloalkanes suitable for use as high-octane, cellulosic gasoline. Analogous electrolysis of an itaconic acid-derived methylsuccinic monoester yields a chiral 2,5-dimethyladipic acid diester, another underutilized monomer owing to lack of availability.

  8. Electrochemical Coupling of Biomass‐Derived Acids: New C8 Platforms for Renewable Polymers and Fuels

    PubMed Central

    Wu, Linglin; Farmer, Thomas J.; Arnaud, Sacha Pérocheau; Wong Chang, Maria‐Angelica

    2016-01-01

    Abstract Electrolysis of biomass‐derived carbonyl compounds is an alternative to condensation chemistry for supplying products with chain length >C6 for biofuels and renewable materials production. Kolbe coupling of biomass‐derived levulinic acid is used to obtain 2,7‐octanedione, a new platform molecule only two low process‐intensity steps removed from raw biomass. Hydrogenation to 2,7‐octanediol provides a chiral secondary diol largely unknown to polymer chemistry, whereas intramolecular aldol condensation followed by hydrogenation yields branched cycloalkanes suitable for use as high‐octane, cellulosic gasoline. Analogous electrolysis of an itaconic acid‐derived methylsuccinic monoester yields a chiral 2,5‐dimethyladipic acid diester, another underutilized monomer owing to lack of availability. PMID:27873475

  9. Electrochemical, interfacial, and surface studies of the conversion of carbon dioxide to liquid fuels on tin electrodes

    NASA Astrophysics Data System (ADS)

    Wu, Jingjie

    maximize the triple phase boundary length for simultaneous high current density and selectivity towards formate formation (Chapter 3). The Sn GDEs was incorporated into a home-designed scalable full electrochemical cell which features a buffer layer of circulating liquid electrolyte mediating the proton concentration at cathode electrode surface. The Sn GDEs exhibited excellent short-term performance for CO2 reduction with high selectivity towards formate formation at low overpotentials in the full electrochemical cell. Additionally, coupling water oxidation and CO2 reduction was demonstrated in this full electrochemical cell to mimic biosynthesis (Chapter 4). The rapid degradation of selectivity towards formate formation on Sn GDEs in the full electrochemical cell, however, was observed during long-term operation. The degradation mechanism was unraveled due to the decrease of electrode potential resulted from substantial increase of internal ohmic resistance of the full electrochemical cell. The unexpected rise of internal ohmic resistance was attributed to the pulverization of 100 nm Sn nanoparticles due to the hydrogen diffusion induced stress. Based on the understanding of the origin of Sn nanoparticles pulverization, SnO2 nanoparticles of 3˜3.5 nm close to the critical size were utilized and reduced in situ to form Sn catalyst for electrochemical reduction of CO2. The pulverization was suppressed and subsequently a stable performance of electrodes was obtained (Chapter 5). Due to the affinity to oxygen, Sn nanoparticle surface is covered by a native thin oxide layer. The performance of Sn GDEs towards CO2 reduction strongly depends on the initial thickness of the surface oxide layer. The selectivity towards formate production dropped while the hydrogen yield increased as the initial thickness of the oxide layer increased (Chapter 6). These results suggest the underlying of surface structure on the selectivity of Sn electrode for CO2 reduction and provide insight into

  10. Comparative spectroscopic and electrochemical study of nitroindazoles: 3-Alcoxy, 3-hydroxy and 3-oxo derivatives

    NASA Astrophysics Data System (ADS)

    Rodríguez, Jorge; Olea-Azar, Claudio; Barriga, German; Folch, Christian; Gerpe, Alejandra; Cerecetto, Hugo; González, Mercedes

    2008-08-01

    Cyclic voltammetry and electron spin resonance techniques were used in the investigation of novel 3-alkoxy- and 3-hydroxy-1-[ω-(dialkylamino)alkyl]-5-nitroindazole derivatives. A self-protonation process involving the protonation of the nitro group was observed. The reactivity of the nitro-anion radical for these derivatives with glutathione, a biological relevant thiol, was also studied by cyclic voltammetry. These studies demonstrated that glutathione could react with radical species from 5-nitroindazole system. Also we demonstrated that nitro-anion radicals show three different patterns of delocalization where the indazole 1-lateral chain does not have major influence.

  11. Seasonal Surface Spectral Emissivity Derived from Terra MODIS Data

    NASA Technical Reports Server (NTRS)

    Sun-Mack, Sunny; Chen, Yan; Minnis, Patrick; Young, DavidF.; Smith, William J., Jr.

    2004-01-01

    The CERES (Clouds and the Earth's Radiant Energy System) Project is measuring broadband shortwave and longwave radiances and deriving cloud properties form various images to produce a combined global radiation and cloud property data set. In this paper, simultaneous data from Terra MODIS (Moderate Resolution Imaging Spectroradiometer) taken at 3.7, 8.5, 11.0, and 12.0 m are used to derive the skin temperature and the surface emissivities at the same wavelengths. The methodology uses separate measurements of clear sky temperature in each channel determined by scene classification during the daytime and at night. The relationships between the various channels at night are used during the day when solar reflectance affects the 3.7- m radiances. A set of simultaneous equations is then solved to derive the emissivities. Global monthly emissivity maps are derived from Terra MODIS data while numerical weather analyses provide soundings for correcting the observed radiances for atmospheric absorption. These maps are used by CERES and other cloud retrieval algorithms.

  12. Effect of the length and surface area on electrochemical performance of cobalt oxide nanowires for alkaline secondary battery application

    NASA Astrophysics Data System (ADS)

    Xu, Yanan; Wang, Xiaofeng; An, Cuihua; Wang, Yijing; Jiao, Lifang; Yuan, Huatang

    2014-12-01

    One-dimensional porous Co3O4 nanowires with different length have been successfully synthesized by thermal decomposition of Co-NA polymer precursors at various hydrothermal reaction times. The positive effects of longer nanowires and larger surface area on electrochemical performance of Co3O4 samples were investigated systematically. All the as-prepared Co3O4 samples display excellent discharge capacities and cycle stability on account of large surface area and porous structure, indicating great potential application of porous Co3O4 nanowires for alkaline rechargeable batteries. The Co3O4-24 h sample with the longest length shows the most outstanding electrochemical performance, and displays the maximum discharge capacity of 450.1 mAh g-1 with the capacity retention of 90.4% after 100 cycles at a current density of 100 mA g-1. Electrochemical reactions between Co and Co(OH)2 occurring on the Co3O4 electrodes are investigated by XRD, cyclic voltammetry (CV) and charge-discharge measurements.

  13. Influence of benzimidazole derivatives on corrosion and electrochemical behavior of iron

    SciTech Connect

    Makovei, G.L.; Keris, L.D.; Kurmakova, I.N.

    1986-03-01

    The authors study the relation of the ..pi..-electron density of the molecules of benzimidazole and its derivatives and their inhibiting effect in hydrochloric acid. The compositions of the derivatives of synthesized benzimidazole were verified by ultimate analysis and IR spectroscopy. The ..pi..-electron densities were calculated on a computer. It was found that the introduction of a proton increases the charge re-distribution in the imidazole and benzene rings, with practically no change in the charge on the substituents. The efficiency of inhibition of corrosion was studied by the gravimetric and potentiodynamic methods. To elucidate the limiting stages of cathodic evolution of hydrogen and anodic solution of the metal, the authors recorded polarization curves for steel St3 without additive and with 20 mM benzimidazole, 1-(alpha-acetoxy)ethylbensimidazole and 1-acetylbenzimidazole. The polarization curves for various concentrations of benzimidazole and its derivatives in the pH range 0-2 and a calculation of the characteristics of the cathodic evolution of hydrogen suggest that the limiting stage of the process is delayed discharge.

  14. Effect of Pd Interlayer on Electrochemical Properties of ENIG Surface Finish in 3.5 wt.% NaCl Solution

    NASA Astrophysics Data System (ADS)

    Nam, N. D.; Bui, Q. V.; Nhan, H. T.; Phuong, D. V.; Bian, M. Z.

    2014-09-01

    The corrosion resistance of a multilayered (NiP-Pd-Au) coating with various thicknesses of palladium (Pd) interlayer deposited on copper by an electroless method was investigated using electrochemical techniques including potentiodynamic polarization and electrochemical impedance spectroscopy. In addition, the surface finish was examined by x-ray diffraction analysis and scanning electron microscopy, and the contact angle of the liquid-solid interface was recorded. The corrosion resistance of the copper substrate was considerably improved by Pd interlayer addition. Increase of the thickness of the Pd interlayer enhanced the performance of the Cu-NiP-Pd-Au coating due to low porosity, high protective efficiency, high charge-transfer resistance, and contact angle. These are attributed to the diffusion of layers in the Cu-NiP-Pd-Au coating acting as a physical barrier layer, leading to the protection provided by the coating.

  15. Electrochemical synthesis of elongated noble metal nanoparticles, such as nanowires and nanorods, on high-surface area carbon supports

    DOEpatents

    Adzic, Radoslav; Blyznakov, Stoyan; Vukmirovic, Miomir

    2015-08-04

    Elongated noble-metal nanoparticles and methods for their manufacture are disclosed. The method involves the formation of a plurality of elongated noble-metal nanoparticles by electrochemical deposition of the noble metal on a high surface area carbon support, such as carbon nanoparticles. Prior to electrochemical deposition, the carbon support may be functionalized by oxidation, thus making the manufacturing process simple and cost-effective. The generated elongated nanoparticles are covalently bound to the carbon support and can be used directly in electrocatalysis. The process provides elongated noble-metal nanoparticles with high catalytic activities and improved durability in combination with high catalyst utilization since the nanoparticles are deposited and covalently bound to the carbon support in their final position and will not change in forming an electrode assembly.

  16. Satellite-Derived Sea Surface Temperature: Workshop 1

    NASA Technical Reports Server (NTRS)

    Njoku, E. G.

    1983-01-01

    Satellite measurements of sea surface temperature are now possible using a variety of sensors. The present accuracies of these methods are in the range of 0.5 to 2.0 C. This makes them potentially useful for synoptic studies of ocean currents and for global monitoring of climatological anomalies. To improve confidence in the satellite data, objective evaluations of sensor accuracies are necessary, and the conditions under which these accuracies degrade need to be understood. The Scanning Multichannel Microwave Radiometer (SMMR) on the Nimbus-7 satellite was studied. Sea surface temperatures, derived from November 1979 SMMR data, were compared globally against ship measurements and climatology, using facilities of the JPL Pilot Ocean Data System. Methods for improved data analysis and plans for additional workshops to incorporate data from other sensors were discussed.

  17. Constraints on the oxidation state of the mantle: An electrochemical and sup 57 Fe Moessbauer study of mantle-derived ilmenites

    SciTech Connect

    Virgo, D.; Luth, R.W. ); Moats, M.A.; Ulmer, G.C. )

    1988-07-01

    Ilmenite samples from four kimberlite localities were studied using electrochemical, Moessbauer spectroscopic, and microprobe analytical techniques in order to infer the oxidation state of their source regions in the mantle. The values of Fe{sup 3+}/{Sigma}Fe calculated from analyses, using three different electron microanalytical instruments assuming ilmenite stoichiometry, are consistently higher than those derived from the Moessbauer data, by as much as 100%. Furthermore, the range in Fe{sup 3+}/{Sigma}Fe calculated using the analyses from different instruments and/or different correction schemes is nearly as large. Thus Fe{sup 3+}/{Sigma}Fe calculated from microprobe analyses should be taken with caution, even if the precision appears high. {sup 57}Fe Moessbauer spectroscopy on the electrochemical experiment run products demonstrates that Fe{sup 3+}/{Sigma}Fe is significantly lower than it is for the natural C-bearing ilmenites. In contrast, the ilmenite that lacked C did not change Fe{sup 3+}/{Sigma}Fe during the electrochemical experiment. Examination of the reduced samples with SEM established that the natural, single-phase ilmenites exsolved during the electrochemical experiment to form ilmenite{sub ss} + spinel{sub ss}. The initial, reduced trends in the electrochemical experiments for the C-bearing ilmenites are attributed to disequilibrium interactions between the decomposing sample and the evolved gas in the electrochemical cell and do not represent the quenched mantle memory nor the intrinsic f{sub O{sub 2}} of the sample prior to reduction. Furthermore, the oxidized f{sub O{sub 2}} trend is interpreted, for the carbon-bearing samples, are representing the f{sub O{sub 2}} of the ilmenite{sub ss} + spinel{sub ss} assemblage and not the intrinsic f{sub o{sub 2}} of the mantle-derived ilemnite{sub ss}.

  18. New electrochemical procedure for obtaining surface enhanced Raman scattering active polythiophene films on platinum

    NASA Astrophysics Data System (ADS)

    Bazzaoui, E. A.; Aeiyach, S.; Aubard, J.; Felidj, N.; Lévi, G.; Sakmeche, N.; Lacaze, P. C.

    1998-06-01

    A new electrochemical procedure for obtaining Surface Enhanced Raman Scattering (SERS) spectra of silver islands polybithiophene composite films is described. During the electropolymerization process which consists to use silver dodecylsulfate micellar aqueous solution mixed with bithiophene and LiClO4, silver cations are reduced, thus giving metallic silver particles embedded within the polybithiophene (PbT) film. Both doped and undoped PbT species display SERS spectra with exaltation factors varying between 40 and 200 with respect to the film prepared in sodium dodecylsulfate. Vibrational characterization of both doped and undoped species show that the amount of the polymer structural defects are more important in the oxidized species than in the reduced ones. This general method allows to synthesize various polymeric films displaying SERS effect and appears very promising for the structural study of these materials. Nous décrivons un procédé original pour synthétiser par voie électrochimique des films formés d'un composite de polybithiophène et d'îlots d'argent qui présentent des Spectres de Diffusion Raman Exaltée de Surface (DRES). Au cours de l'électropolymérisation d'une solution aqueuse micellaire de bithiophène en présence de dodécylsulfate d'argent (AgDS) et de LiClO4, les ions argent présents dans la solution se complexent avec le soufre du bithiophène et pénètrent dans le film polymère où ils sont réduits sous forme d'argent métallique. Les spectres Raman des deux formes réduite et oxydée du film ainsi obtenu présentent un effet DRES important avec un facteur d'exaltation variant entre 40 et 200 par rapport au même film électrosynthétisé en présence de dodécylsulfate de sodium (SDS). L'analyse vibrationnelle des deux formes redox montre que le taux de défauts est plus important dans la forme oxydée que dans la forme réduite. Cette méthode de polymérisation très générale, qui permet d'obtenir des polymères

  19. Electrochemical Cathodic Polarization, a Simplified Method That Can Modified and Increase the Biological Activity of Titanium Surfaces: A Systematic Review

    PubMed Central

    2016-01-01

    Background The cathodic polarization seems to be an electrochemical method capable of modifying and coat biomolecules on titanium surfaces, improving the surface activity and promoting better biological responses. Objective The aim of the systematic review is to assess the scientific literature to evaluate the cellular response produced by treatment of titanium surfaces by applying the cathodic polarization technique. Data, Sources, and Selection The literature search was performed in several databases including PubMed, Web of Science, Scopus, Science Direct, Scielo and EBSCO Host, until June 2016, with no limits used. Eligibility criteria were used and quality assessment was performed following slightly modified ARRIVE and SYRCLE guidelines for cellular studies and animal research. Results Thirteen studies accomplished the inclusion criteria and were considered in the review. The quality of reporting studies in animal models was low and for the in vitro studies it was high. The in vitro and in vivo results reported that the use of cathodic polarization promoted hydride surfaces, effective deposition, and adhesion of the coated biomolecules. In the experimental groups that used the electrochemical method, cellular viability, proliferation, adhesion, differentiation, or bone growth were better or comparable with the control groups. Conclusions The use of the cathodic polarization method to modify titanium surfaces seems to be an interesting method that could produce active layers and consequently enhance cellular response, in vitro and in vivo animal model studies. PMID:27441840

  20. Lunar surface roughness derived from LRO Diviner Radiometer observations

    NASA Astrophysics Data System (ADS)

    Bandfield, Joshua L.; Hayne, Paul O.; Williams, Jean-Pierre; Greenhagen, Benjamin T.; Paige, David A.

    2015-03-01

    Sunlit and shaded slopes have a variety of temperatures based on their orientation with respect to the Sun. Generally, greater slope angles lead to higher anisothermality within the field of view. This anisothermality is detected by measuring changing emitted radiance as a function of viewing angle or by measuring the difference in brightness temperatures with respect to observation wavelength. Thermal infrared measurements from the Lunar Reconnaissance Orbiter Diviner Radiometer were used to derive lunar surface roughness via two observation types: (1) nadir multispectral observations with full diurnal coverage and (2) multiple emission angle targeted observations. Measurements were compared to simulated radiance from a radiative equilibrium thermal model and Gaussian slope distribution model. Nadir observations most closely match a 20° RMS slope distribution, and multiple emission angle observations can be modeled using 20-35° RMS slope distributions. Limited sampling of the lunar surface did not show any clear variation in roughness among surface units. Two-dimensional modeling shows that surfaces separated by distances greater than 0.5-5 mm can remain thermally isolated in the lunar environment, indicating the length scale of the roughness features. Non-equilibrium conditions are prevalent at night and near sunrise and sunset, preventing the use of the equilibrium thermal model for roughness derivations using data acquired at these local times. Multiple emission angle observations also show a significant decrease in radiance at high emission angles in both daytime and nighttime observations, and hemispherical emissivity is lower than is apparent from nadir observations. These observations and models serve as a basis for comparison with similar measurements of other airless bodies and as an initial template for the interpretation of TIR measurements acquired under a variety of geometric conditions.

  1. Improvement of the Electrochemical Behavior of Steel Surfaces Using a [Ti-Al/Ti-Al-N] n Multilayer System

    NASA Astrophysics Data System (ADS)

    Ipaz, L.; Aperador, W.; Caicedo, J. C.; Esteve, J.; Zambrano, G.

    2013-05-01

    The aim of this work is to improve the corrosion resistance of AISI D3 steel surfaces using a [Ti-Al/Ti-Al-N] n multilayer system deposited with different periods (Λ) and bilayer numbers ( n), via magnetron co-sputtering pulsed d.c. procedure, from a metallic (Ti-Al) binary target. The multilayer coatings were characterized by cross-sectional scanning electron microscopy that showed the modulation and microstructure of the [Ti-Al/Ti-Al-N] n multilayer system. The composition of the single Ti-Al and Ti-Al-N layer films was studied via x-ray photoelectron spectroscopy, where typical signals for Ti2p1/2, Ti2p, N1s, and Al2p3/2 were detected. The electrochemical properties were evaluated by electrochemical impedance spectroscopy and Tafel polarization curves. The optimal electrochemical behavior was obtained for the [Ti-Al/Ti-Al-N] n multilayered period of Λ = 25 nm (100 bilayers). At these conditions, the maximum polarization resistance (1719.32 kΩ cm2) and corrosion rate (0.7 μmy) were 300 and 35 times higher than that of uncoated AISI D3 steel substrate (5.61 kΩ cm2 and 25 μmy, respectively). Finally, scanning electron microscopy was used to analyze the [Ti-Al/Ti-Al-N] n multilayered surface after the corrosive attack. The improvement effects in the electrochemical behavior of the AISI D3 coated with the [Ti-Al/Ti-Al-N] n multilayered coatings could be attributed to the number of interfaces that act as obstacles for the inward and outward diffusions of Cl- ions, generating an increment in the energy or potential required for translating the corrosive ions across the coating/substrate interface.

  2. Tunable Electrochemical and Catalytic Features of BIAN- and BIAO-Derived Ruthenium Complexes.

    PubMed

    Hazari, Arijit Singha; Das, Ankita; Ray, Ritwika; Agarwala, Hemlata; Maji, Somnath; Mobin, Shaikh M; Lahiri, Goutam Kumar

    2015-05-18

    This article deals with a class of ruthenium-BIAN-derived complexes, [Ru(II)(tpm)(R-BIAN)Cl]ClO4 (tpm = tris(1-pyrazolyl)methane, R-BIAN = bis(arylimino)acenaphthene, R = 4-OMe ([1a]ClO4), 4-F ([1b]ClO4), 4-Cl ([1c]ClO4), 4-NO2 ([1d]ClO4)) and [Ru(II)(tpm)(OMe-BIAN)H2O](2+) ([3a](ClO4)2). The R-BIAN framework with R = H, however, leads to the selective formation of partially hydrolyzed BIAO ([N-(phenyl)imino]acenapthenone)-derived complex [Ru(II)(tpm)(BIAO)Cl]ClO4 ([2]ClO4). The redox-sensitive bond parameters involving -N═C-C═N- or -N═C-C═O of BIAN or BIAO in the crystals of representative [1a]ClO4, [3a](PF6)2, or [2]ClO4 establish its unreduced form. The chloro derivatives 1a(+)-1d(+) and 2(+) exhibit one oxidation and successive reduction processes in CH3CN within the potential limit of ±2.0 V versus SCE, and the redox potentials follow the order 1a(+) < 1b(+) < 1c(+) < 1d(+) ≈ 2(+). The electronic structural aspects of 1a(n)-1d(n) and 2(n) (n = +2, +1, 0, -1, -2, -3) have been assessed by UV-vis and EPR spectroelectrochemistry, DFT-calculated MO compositions, and Mulliken spin density distributions in paramagnetic intermediate states which reveal metal-based (Ru(II) → Ru(III)) oxidation and primarily BIAN- or BIAO-based successive reduction processes. The aqua complex 3a(2+) undergoes two proton-coupled redox processes at 0.56 and 0.85 V versus SCE in phosphate buffer (pH 7) corresponding to {Ru(II)-H2O}/{Ru(III)-OH} and {Ru(III)-OH}/{Ru(IV)═O}, respectively. The chloro (1a(+)-1d(+)) and aqua (3a(2+)) derivatives are found to be equally active in functioning as efficient precatalysts toward the epoxidation of a wide variety of alkenes in the presence of PhI(OAc)2 as oxidant in CH2Cl2 at 298 K, though the analogous 2(+) remains virtually inactive. The detailed experimental analysis with the representative precatalyst 1a(+) suggests the involvement of the active {Ru(IV)═O} species in the catalytic cycle, and the reaction proceeds through the

  3. Ultrathin nickel hydroxide nanosheet arrays grafted biomass-derived honeycomb-like porous carbon with improved electrochemical performance as a supercapacitive material

    NASA Astrophysics Data System (ADS)

    Nagaraju, Goli; Cha, Sung Min; Yu, Jae Su

    2017-03-01

    Three-dimensional hierarchical honeycomb-like activated porous carbon pillared ultrathin Ni(OH)2 nanosheets (Ni(OH)2 NSs@HAPC) for use as supercapacitor materials were facilely synthesized. With an aid of pine cone flowers as a biomass source, HAPC conducting scaffolds were prepared by the alkali treatment and pyrolysis methods under an inert gas atmosphere. Subsequently, the Ni(OH)2 NSs were synthesized evenly on the surface of HAPC via a solvothermal method. The resulting HAPC and Ni(OH)2 NSs@HAPC composite materials offered free pathways for effective diffusion of electrolyte ions and fast transportation of electrons when employed as an electrode material. The Ni(OH)2 NSs@HAPC composite electrode exhibited excellent electrochemical properties including a relatively high specific capacitance (Csp) value of ~ 916.4 F/g at 1 A/g with good cycling stability compared to the pristine HAPC and Ni(OH)2 NSs electrodes. Such bio-friendly derived carbon-based materials with transition metal hydroxide/oxide composite materials could be a promising approach for high-performance energy storage devices because of their advantageous properties of cost effectiveness and easy availability.

  4. Hierarchical structured carbon derived from bagasse wastes: A simple and efficient synthesis route and its improved electrochemical properties for high-performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Feng, Haobin; Hu, Hang; Dong, Hanwu; Xiao, Yong; Cai, Yijin; Lei, Bingfu; Liu, Yingliang; Zheng, Mingtao

    2016-01-01

    Bagasse-derived hierarchical structured carbon (BDHSC) with tunable porosity and improved electrochemical performance is prepared via simple and efficient hydrothermal carbonization combined with KOH activation. Experimental results show that sewage sludge acts as a cheap and efficient structure-directing agent to regulate the morphology, adjust the porosity, and thus improve the supercapacitive performance of BDHSC. The as-resulted BDHSC exhibits an interconnected framework with high specific surface area (2296 m2 g-1), high pore volume (1.34 cm3 g-1), and hierarchical porosity, which offer a more favorable pathway for electrolyte penetration and transportation. Compared to the product obtained from bagasse without sewage sludge, the unique interconnected BDHSC exhibits enhanced supercapacitive performances such as higher specific capacitance (320 F g-1), and better rate capability (capacitance retention over 70.8% at a high current density of 50 A g-1). Moreover, the BDHSC-based symmetric supercapacitor delivers a maximum energy density of over 20 Wh kg-1 at 182 W kg-1 and presents an excellent long-term cycling stability. The developed approach in the present work can be useful not only in production of a variety of novel hierarchical structured carbon with promising applications in high-performance energy storage devices, but also in high-value utilization of biomass wastes and high-ash-content sewage sludge.

  5. Ultrathin nickel hydroxide nanosheet arrays grafted biomass-derived honeycomb-like porous carbon with improved electrochemical performance as a supercapacitive material

    PubMed Central

    Nagaraju, Goli; Cha, Sung Min; Yu, Jae Su

    2017-01-01

    Three-dimensional hierarchical honeycomb-like activated porous carbon pillared ultrathin Ni(OH)2 nanosheets (Ni(OH)2 NSs@HAPC) for use as supercapacitor materials were facilely synthesized. With an aid of pine cone flowers as a biomass source, HAPC conducting scaffolds were prepared by the alkali treatment and pyrolysis methods under an inert gas atmosphere. Subsequently, the Ni(OH)2 NSs were synthesized evenly on the surface of HAPC via a solvothermal method. The resulting HAPC and Ni(OH)2 NSs@HAPC composite materials offered free pathways for effective diffusion of electrolyte ions and fast transportation of electrons when employed as an electrode material. The Ni(OH)2 NSs@HAPC composite electrode exhibited excellent electrochemical properties including a relatively high specific capacitance (Csp) value of ~ 916.4 F/g at 1 A/g with good cycling stability compared to the pristine HAPC and Ni(OH)2 NSs electrodes. Such bio-friendly derived carbon-based materials with transition metal hydroxide/oxide composite materials could be a promising approach for high-performance energy storage devices because of their advantageous properties of cost effectiveness and easy availability. PMID:28338067

  6. ICESat-derived inland water surface spot heights

    NASA Astrophysics Data System (ADS)

    O'Loughlin, Fiachra E.; Neal, Jeffrey; Yamazaki, Dai; Bates, Paul D.

    2016-04-01

    Accurate measurement of water surface height is key to many fields in hydrology and limnology. Satellite radar and laser altimetry have been shown to be useful means of obtaining such data where no ground gauging stations exist, and the accuracy of different satellite instruments is now reasonably well understood. Past validation studies have shown water surface height data from the ICESat instrument to have the highest vertical accuracy (mean absolute errors of ˜10 cm for ICESat, compared, for example, with ˜28 cm from Envisat), yet no freely available source of processed ICESat data currently exists for inland water bodies. Here we present a database of processed and quality checked ICESat-derived inland water surface heights (IWSH) for water bodies greater than 3 arc sec (˜92 m at the equator) in width. Four automated methods for removing spurious observations or outliers were investigated, along with the impact of using different water masks. We find that the best performing method ensures that observations used are completely surrounded by water in the SRTM Water Body data. Using this method for removing spurious observations, we estimate transect-averaged water surface heights at 587,292 unique locations from 2003 to 2009, with the number of locations proportional to the size of the river.

  7. Electrochemically deposited gold nanoparticles on a carbon paste electrode surface for the determination of mercury.

    PubMed

    Sahoo, Srikant; Satpati, Ashis Kumar; Reddy, Annareddy Venkata Ramana

    2015-01-01

    An electrochemical method was developed for the determination of Hg at ultratrace levels using an Au nanoparticle (AuNP) array modified carbon paste electrode (CPE) by anodic stripping voltammetry. Scanning electron microscopy measurements imaged the size and shape of AuNPs on the CPE substrate; it was possible to tune the size and the NP density by changing the deposition time and medium. Electrochemical characterization of the AuNP modified CPE was carried out using cyclic voltammetry and electrochemical impedance measurements. Interferences due to some commonly occurring metal ions and surfactants on the stripping peak of Hg were also investigated. The 3σ detection limit for Hg using the AuNP modified electrode was as 0.24 μg/L. This method was applied to determine Hg in soil samples.

  8. High Power Electrochemical Capacitors

    DTIC Science & Technology

    2012-03-23

    electrochemical properties of vanadium oxide aerogels prepared by a freeze-drying process. Journal of the Electrochemical Society, 2004. 151(5): p...Electrochemical Society, 2002. 149(1): p. A26-A30. 12. Rolison, D.R. and B. Dunn, Electrically conductive oxide aerogels : new materials in...surface area vanadium oxide aerogels . Electrochemical and Solid-State Letters, 2000. 3(10): p. 457-459. 14. Shembel, E., et al., Synthesis, investigation

  9. Validating surface energy balance fluxes derived from airborne remote sensing

    NASA Astrophysics Data System (ADS)

    Chavez Eguez, Jose Luis

    Remote sensing-derived energy balance components were compared against measured eddy covariance energy balance terms using heat flux source area models to validate the airborne multispectral remote sensing procedure in the estimation of instantaneous and daily evapotranspiration rates. A procedure was developed to generate raster layers of the footprint weights for weighting/integrating the different components of the energy balance model and obtain meaningful comparisons to similar energy balance terms measured at eddy covariance and/or Bowen ratio stations. Soil heat flux and surface aerodynamic temperature models were studied in an effort to improve the remote sensing estimation of distributed evapotranspiration rates. Aerial and ground data were acquired over a riparian corridor (Salt Cedar, Tamarix grove), soybean and cornfields (rainfed crops) in different ecosystems. The results confirmed that net radiation is well estimated with the remote sensing technique showing an estimation error of only -4.8 +/- 20.7 W m-2, (-0.5 +/- 3.6%). Linear and exponential soil heat flux models were found to correlate strongly to leaf area index and net radiation. The surface aerodynamic temperature term in the sensible heat flux equation was parameterized using surface radiometric temperature, air temperature, wind speed, and leaf area index. It is suggested that the surface aerodynamic temperature model be tested for a wide range of vegetation types, atmospheric stability conditions, surface heterogeneity, and ecosystems to assess the model limitations. The flux source area footprint model "FSAM" integrated heat flux pixels that compared better to measured values and it is recommended as a standard procedure to compare airborne remote sensing-derived heat fluxes against measured fluxes by eddy covariance systems; when compared to the "FASOWG" footprint model and simple arithmetic averages. Finally, the method that uses alfalfa reference daily evapotranspiration in

  10. In situ anodization of aluminum surfaces studied by x-ray reflectivity and electrochemical impedance spectroscopy

    SciTech Connect

    Bertram, F. Evertsson, J.; Messing, M. E.; Mikkelsen, A.; Lundgren, E.; Zhang, F.; Pan, J.; Carlà, F.; Nilsson, J.-O.

    2014-07-21

    We present results from the anodization of an aluminum single crystal [Al(111)] and an aluminum alloy [Al 6060] studied by in situ x-ray reflectivity, in situ electrochemical impedance spectroscopy and ex situ scanning electron microscopy. For both samples, a linear increase of oxide film thickness with increasing anodization voltage was found. However, the slope is much higher in the single crystal case, and the break-up of the oxide film grown on the alloy occurs at a lower anodization potential than on the single crystal. The reasons for these observations are discussed as are the measured differences observed for x-ray reflectivity and electrochemical impedance spectroscopy.

  11. Novel redox species polyaniline derivative-Au/Pt as sensing platform for label-free electrochemical immunoassay of carbohydrate antigen 199.

    PubMed

    Wang, Liyuan; Shan, Jiao; Feng, Feng; Ma, Zhanfang

    2016-03-10

    A novel electrochemical redox-active nanocomposite was synthesized by a one-pot method using N,N'-diphenyl-p-phenylediamine as monomer, and HAuCl4 and K2PtCl4 as co-oxidizing agents. The as-prepared poly(N,N'-diphenyl-p-phenylediamine)-Au/Pt exhibited admirable electrochemical redox activity at 0.15 V, excellent H2O2 electrocatalytic ability and favorable electron transfer ability. Based on these, the evaluation of the composite as sensing substrate for label-free electrochemical immunosensing to the sensitive detection of carbohydrate antigen 199 was described. This technique proved to be a prospective detection tool with a wide liner range from 0.001 U mL(-1) to 40 U mL(-1), and a low detection limit of 2.3 × 10(-4) U mL(-1) (S/N = 3). In addition, this method was used for the analysis of human serum sample, and good agreement was obtained between the values and those of enzyme-linked immunosorbent assay, implying the potential application in clinical research. Importantly, the strategy of the present substrate could be extended to other polymer-based nanocomposites such as polypyrrole derivatives or polythiophene derivatives, and this could be of great significance for the electrochemical immunoassay.

  12. Electrochemical capacitor

    DOEpatents

    Anderson, Marc A.; Liu, Kuo -Chuan; Mohr, Charles M.

    1999-10-05

    An inexpensive porous metal oxide material having high surface area, good conductivity and high specific capacitance is advantageously used in an electrochemical capacitor. The materials are formed in a sol-gel process which affords control over the properties of the resultant metal oxide materials.

  13. Synthesis, spectroscopic characterization, electrochemical behaviour and thermal decomposition studies of some transition metal complexes with an azo derivative

    NASA Astrophysics Data System (ADS)

    Sujamol, M. S.; Athira, C. J.; Sindhu, Y.; Mohanan, K.

    2010-01-01

    Complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) with a novel heterocyclic azo derivative, formed by coupling diazotized 2-amino-3-carbethoxy-4,5-dimethylthiophene with acetylacetone were synthesized and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, UV-vis, IR, 1H NMR and EPR spectral data. Spectral studies revealed that the ligand existed in an internally hydrogen bonded azo-enol form rather than the keto-hydrazone form and coordinated to the metal ion in a tridentate fashion. Analytical data revealed that all the complexes exhibited 1:1 metal-ligand ratio. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry was proposed for each complex. The nickel(II) complex has undergone facile transesterification reaction when refluxed in methanol for a long period. The ligand and the copper(II) complex were subjected to X-ray diffraction study. The electrochemical behaviour of copper(II) complex was investigated by cyclic voltammetry. The thermal behaviour of the same complex was also examined by thermogravimetry.

  14. Synthesis, spectroscopic characterization, electrochemical behaviour and thermal decomposition studies of some transition metal complexes with an azo derivative.

    PubMed

    Sujamol, M S; Athira, C J; Sindhu, Y; Mohanan, K

    2010-01-01

    Complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) with a novel heterocyclic azo derivative, formed by coupling diazotized 2-amino-3-carbethoxy-4,5-dimethylthiophene with acetylacetone were synthesized and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, UV-vis, IR, (1)H NMR and EPR spectral data. Spectral studies revealed that the ligand existed in an internally hydrogen bonded azo-enol form rather than the keto-hydrazone form and coordinated to the metal ion in a tridentate fashion. Analytical data revealed that all the complexes exhibited 1:1 metal-ligand ratio. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry was proposed for each complex. The nickel(II) complex has undergone facile transesterification reaction when refluxed in methanol for a long period. The ligand and the copper(II) complex were subjected to X-ray diffraction study. The electrochemical behaviour of copper(II) complex was investigated by cyclic voltammetry. The thermal behaviour of the same complex was also examined by thermogravimetry.

  15. The Influence of Electrolytic Concentration on the Electrochemical Deposition of Calcium Phosphate Coating on a Direct Laser Metal Forming Surface

    PubMed Central

    Yang, Yuhui; Luo, Wenjing

    2017-01-01

    A calcium phosphate (CaP) coating on titanium surface enhances its biocompatibility, thus facilitating osteoconduction and osteoinduction with the inorganic phase of the human bone. Electrochemical deposition has been suggested as an effective means of fabricating CaP coatings on porous surface. The purpose of this study was to develop CaP coatings on a direct laser metal forming implant using electrochemical deposition and to investigate the effect of electrolytic concentration on the coating's morphology and structure by X-ray diffraction, scanning electron microscopy, water contact angle analysis, and Fourier transform infrared spectroscopy. In group 10−2, coatings were rich in dicalcium phosphate, characterized to be thick, layered, and disordered plates. In contrast, in groups 10−3 and 10−4, the relatively thin and well-ordered coatings predominantly consisted of granular hydroxyapatite. Further, the hydrophilicity and cell affinity were improved as electrolytic concentration increased. In particular, the cells cultured in group 10−3 appeared to have spindle morphology with thick pseudopodia on CaP coatings; these spindles and pseudopodia strongly adhered to the rough and porous surface. By analyzing and evaluating the surface properties, we provided further knowledge on the electrolytic concentration effect, which will be critical for improving CaP coated Ti implants in the future. PMID:28250771

  16. Derivation of surface properties from Magellan altimetry data

    NASA Technical Reports Server (NTRS)

    Lovell, Amy J.; Schloerb, F. Peter; Mcgill, George E.

    1992-01-01

    The fit of the Hagfors model to the Magellan altimetry data provides a means to characterize the surface properties of Venus. However, the derived surface properties are only meaningful if the model provides a good representation of the data. The Hagfors model provides a good representation of the data. The Hagfors model is generally a realistic fit to surface scattering properties of a nadir-directed antenna such as the Magellan altimeter; however, some regions of the surface of Venus are poorly described by the existing model, according to the goodness of fit parameter provided on the ARCDR CD-ROMs. Poorly characterized regions need to be identified and fit to new models in order to derive more accurate surface properties for use in inferring the geological processes that affect the surface in those regions. We have compared the goodness of fit of the Hagfors model to the distribution of features across the planet, and preliminary results show a correlation between steep topographic slopes and poor fits to the standard model, as has been noticed by others. In this paper, we investigate possible relations between many classes of features and the ability of the Hagfors model to fit the observed echo profiles. In the regions that are not well characterized by existing models, we calculate new models that compensate for topographic relief in order to derive improved estimates of surface properties. Areas investigated to date span from longitude 315 through 45, at all latitudes covered by Magellan. A survey of those areas yields preliminary results that suggest that topographically high regions are well suited to the current implementation of the Hagfors model. Striking examples of such large-scale good fits are Alpha Regio, the northern edges of Lada Terra, and the southern edge of Ishtar Terra. Other features that are typically well fit are the rims of coronae such as Heng-O and the peaks of volcanos such as Gula Mons. Surprisingly, topographically low regions, such

  17. Derivation of surface properties from Magellan altimetry data

    NASA Astrophysics Data System (ADS)

    Lovell, Amy J.; Schloerb, F. Peter; McGill, George E.

    1992-12-01

    The fit of the Hagfors model to the Magellan altimetry data provides a means to characterize the surface properties of Venus. However, the derived surface properties are only meaningful if the model provides a good representation of the data. The Hagfors model provides a good representation of the data. The Hagfors model is generally a realistic fit to surface scattering properties of a nadir-directed antenna such as the Magellan altimeter; however, some regions of the surface of Venus are poorly described by the existing model, according to the goodness of fit parameter provided on the ARCDR CD-ROMs. Poorly characterized regions need to be identified and fit to new models in order to derive more accurate surface properties for use in inferring the geological processes that affect the surface in those regions. We have compared the goodness of fit of the Hagfors model to the distribution of features across the planet, and preliminary results show a correlation between steep topographic slopes and poor fits to the standard model, as has been noticed by others. In this paper, we investigate possible relations between many classes of features and the ability of the Hagfors model to fit the observed echo profiles. In the regions that are not well characterized by existing models, we calculate new models that compensate for topographic relief in order to derive improved estimates of surface properties. Areas investigated to date span from longitude 315 through 45, at all latitudes covered by Magellan. A survey of those areas yields preliminary results that suggest that topographically high regions are well suited to the current implementation of the Hagfors model. Striking examples of such large-scale good fits are Alpha Regio, the northern edges of Lada Terra, and the southern edge of Ishtar Terra. Other features that are typically well fit are the rims of coronae such as Heng-O and the peaks of volcanos such as Gula Mons. Surprisingly, topographically low regions, such

  18. Surface aspects of sol-gel derived hematite films for the photoelectrochemical oxidation of water.

    PubMed

    Herrmann-Geppert, Iris; Bogdanoff, Peter; Radnik, Jörg; Fengler, Steffen; Dittrich, Thomas; Fiechter, Sebastian

    2013-02-07

    α-Fe(2)O(3) (hematite) photoanodes for the oxygen evolution reaction (OER) were prepared by a cost-efficient sol-gel procedure. Due to low active photoelectrochemical properties observed, it is assumed that the sol-gel procedure leads to hematite films with defects and surface states on which generated charge carriers are recombined or immobilized in trap processes. Electrochemical activation was proven to diminish unfavourable surface groups to some extent. More efficiently, a plasma treatment improves significantly the photoelectrochemical properties of the OER. X-ray photoelectron spectroscopy (XPS) analysis reveals an oxygen enriched surface layer with new oxygen species which may be responsible for the improved electrochemical activity. Due to surface photovoltage an increased fraction of transferred charge carriers from these newly produced surface defects are identified.

  19. Inhibition of Electrochemical Reactions at Gold Surfaces by Grafted, Highly Fluorinated, Hyperbranched Polymer Films

    DTIC Science & Technology

    1996-10-01

    50 atom% F; These films are very hydrophobic (water contact angle of 114 deg) and block electrochemical reactions on gold electrodes. Cyclic ... voltammetry in basic solution shows that while an electrode covered with a 3-layer PAA (3-PAA) film mimics an assembly of microelectrodes, a fluorinated 3

  20. The Significance of Electrochemical Activation Parameters for Surface-Attached Reactants.

    DTIC Science & Technology

    1982-11-18

    interesting 7 8 results for the ferrocene /ferricinium couple bound to a platinum electrode. Values of k* for this couple were reported as a function of...S.W. Barr, M.J. Weaver, in "Proc. Symp. on Electrocatalysis ", W.E. O’Grady, P.N. Ross Jr., F.G. Will (eds), The Electrochemical Society, Pennington

  1. The EChemPen: A Guiding Hand to Learn Electrochemical Surface Modifications

    ERIC Educational Resources Information Center

    Valetaud, Mathieu; Loget, Gabriel; Roche, Je´rome; Hu¨sken, Nina; Fattah, Zahra; Badets, Vasilica; Fontaine, Olivier; Zigah, Dodzi

    2015-01-01

    The Electrochemical Pen (EChemPen) was developed as an attractive tool for learning electrochemistry. The fabrication, principle, and operation of the EChemPen are simple and can be easily performed by students in practical classes. It is based on a regular fountain pen principle, where the electrolytic solution is dispensed at a tip to locally…

  2. Synthesis, photophysical, and electrochemical properties of wide band gap tetraphenylsilane-carbazole derivatives: Effect of the substitution position and naphthalene side chain

    NASA Astrophysics Data System (ADS)

    Ho, Kar Wei; Ariffin, A.

    2016-12-01

    Four tetraphenylsilane-carbazole derivatives with wide bandgaps (3.38-3.55 eV) were synthesized. The effects of the substitution position and of the presence of naphthalene groups on the photophysical, electrochemical and thermal properties were investigated. The derivatives exhibited maximum absorption peaks ranging from 293 to 304 nm and maximum emission peaks ranging from 347 to 386 nm. Changing the carbazole substitution position on the tetraphenylsilane did not significantly change the photophysical and electrochemical properties. However, p-substituted compounds exhibited higher glass transition temperatures than m-substituted compounds. Naphthalene groups with bulky structures had extended the conjugation lengths that red-shifted both the absorption and emission spectra. The LUMO level was decreased, which reduced the optical bandgap and triplet energy level. However, the naphthalene groups significantly improved the thermal stability by increasing the glass transition temperature of the compounds.

  3. Universal Dynamic DNA Assembly-Programmed Surface Hybridization Effect for Single-Step, Reusable, and Amplified Electrochemical Nucleic Acid Biosensing.

    PubMed

    Liu, Shufeng; Fang, Li; Wang, Yanqun; Wang, Li

    2017-03-07

    The traditional sensitive electrochemical biosensors are commonly confronted with the cumbersome interface operation and washing procedures and the inclusion of extra exogenous reagents, which impose the challenge on the detection simplicity, reliability, and reusability. Herein, we present the proof-of-principle of a unique biosensor architecture based on dynamic DNA assembly programmed surface hybridization, which confers the single-step, reusable, and enzyme-free amplified electrochemical nucleic acid analysis. To demonstrate the fabrication universality three dynamic DNA assembly strategies including DNA-fueled target recycling, catalytic hairpin DNA assembly, and hybridization chain reaction were flexibly harnessed to convey the homogeneous target recognition and amplification events into various DNA scaffolds for the autonomous proximity-based surface hybridization. The current biosensor architecture features generalizability, simplicity, low cost, high sensitivity, and specificity over the traditional nucleic acid-related amplified biosensors. The lowest detection limit of 50 aM toward target DNA could be achieved by hybridization chain reaction-programmed surface hybridization. The reliable working ability for both homogeneous solution and heterogeneous inteface facilitates the target analysis with a robust reliability and reproducibility, also making it to be readily extended for the integration with the kinds of detecting platforms. Thus, it may hold great potential for the biosensor fabrication served for the point-of-care applications in resource constrained regions.

  4. Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices.

    PubMed

    Soliman, Ahmed B; Abdel-Samad, Hesham S; Abdel Rehim, Sayed S; Hassan, Hamdy H

    2016-02-26

    Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results.

  5. Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices

    PubMed Central

    Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Hassan, Hamdy H.

    2016-01-01

    Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results. PMID:26916054

  6. Synthesis and electrochemical performance of surface-modified nano-sized core/shell tin particles for lithium ion batteries.

    PubMed

    Schmuelling, Guido; Oehl, Nikolas; Knipper, Martin; Kolny-Olesiak, Joanna; Plaggenborg, Thorsten; Meyer, Hinrich-Wilhelm; Placke, Tobias; Parisi, Jürgen; Winter, Martin

    2014-09-05

    Tin is able to lithiate and delithiate reversibly with a high theoretical specific capacity, which makes it a promising candidate to supersede graphite as the state-of-the-art negative electrode material in lithium ion battery technology. Nevertheless, it still suffers from poor cycling stability and high irreversible capacities. In this contribution, we show the synthesis of three different nano-sized core/shell-type particles with crystalline tin cores and different amorphous surface shells consisting of SnOx and organic polymers. The spherical size and the surface shell can be tailored by adjusting the synthesis temperature and the polymer reagents in the synthesis, respectively. We determine the influence of the surface modifications with respect to the electrochemical performance and characterize the morphology, structure, and thermal properties of the nano-sized tin particles by means of high-resolution transmission electron microscopy, x-ray diffraction, and thermogravimetric analysis. The electrochemical performance is investigated by constant current charge/discharge cycling as well as cyclic voltammetry.

  7. Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices

    NASA Astrophysics Data System (ADS)

    Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Hassan, Hamdy H.

    2016-02-01

    Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results.

  8. Electrochemical synthesis of gold nanoparticles on the surface of multi-walled carbon nanotubes with glassy carbon electrode and their application

    NASA Astrophysics Data System (ADS)

    Song, Y. Z.; Li, X.; Song, Y.; Cheng, Z. P.; Zhong, H.; Xu, J. M.; Lu, J. S.; Wei, C. G.; Zhu, A. F.; Wu, F. Y.; Xu, J.

    2013-01-01

    Gold nanoparticles on the surface of multi-walled carbon nanotubes with glassy carbon electrode were prepared using electrochemical synthesis method. The thin films of gold Nanoparticles/multi-walled carbon nanotubes were characterized by scanning electron microscopy, powder X-ray diffraction, and cyclic voltammetry. Electrochemical behavior of adrenaline hydrochloride at gold nanoparticles/multi-walled carbon nanotube modified glassy carbon electrode was investigated. A simple, sensitive, and inexpensive method for determination of adrenaline hydrochloride was proposed.

  9. Global Surface Thermal Inertia Derived from Dawn VIR Observations

    NASA Astrophysics Data System (ADS)

    Titus, T. N.; Becker, K. J.; Anderson, J.; Capria, M.; Tosi, F.; Prettyman, T. H.; De Sanctis, M. C.; Palomba, E.; Grassi, D.; Capaccioni, F.; Ammannito, E.; Combe, J.; McCord, T. B.; Li, J. Y.; Russell, C. T.; Raymond, C. A.

    2012-12-01

    Comparisons of surface temperatures, derived from Dawn [1] Visible and Infrared Mapping Spectrometer (VIR-MS) [2] observations , to thermal models suggest that Vesta generally has a low-thermal-inertia surface, between 25 and 35 J m^-2 K^-1 s^-½, consistent with a thick layer of fine-grain material [3]. Temperatures were calculated using a Bayesian approach to nonlinear inversion as described by Tosi et al. [4]. In order to compare observed temperatures of Vesta to model calculations, several geometric and photometric parameters must be known or estimated. These include local mean solar time, latitude, local slope, bond bolometric albedo, and the effective emissivity at 5μm. Local time, latitude, and local slope are calculated using the USGS ISIS software system [5]. We employ a multi-layered thermal-diffusion model called 'KRC' [6], which has been used extensively in the study of Martian thermophysical properties. This thermal model is easily modified for use with Vesta by replacing the Martian ephemeris input with the Vesta ephemeris and disabling the atmosphere. This model calculates surface temperatures throughout an entire Vesta year for specific sets of slope, azimuth, latitude and elevation, and a range of albedo and thermal-inertia values. The ranges of albedo and thermal inertia values create temperature indices that are closely matched to the dates and times observed by VIR. Based on observed temperatures and best-fit KRC thermal models, estimates of the annual mean surface temperatures were found to range from 176 K - 188 K for flat zenith-facing equatorial surfaces, but these temperatures can drop as low as 112 K for polar-facing slopes at mid-latitudes. [7] In this work, we will compare observed temperatures of the surface of Vesta (using data acquired by Dawn VIR-MS [2] during the approach, survey, high-altitude mapping and departure phases) to model temperature results using the KRC thermal model [5]. Where possible, temperature observations from

  10. Photo-induced electrochemical anodization of p-type silicon: achievement and demonstration of long term surface stability.

    PubMed

    Dhanekar, Saakshi; Islam, S S; Harsh

    2012-06-15

    Surface stability is achieved and demonstrated by porous silicon (PS) fabricated using a wavelength-dependent photo-electrochemical (PEC) anodization technique. During anodization, the photon flux for all wavelengths was kept constant while only the effect of light wavelength on the surface morphology of PS was investigated. PS optical sensors were realized, characterized and tested using a photoluminescence (PL) quenching technique. An aliphatic chain of alcohols (methanol to n-octanol) was detected in the range of 10-200 ppm. Long term surface stability was observed from samples prepared under red (750-620 nm) and green illumination (570-495 nm), where the PL quenching cycles evoke the possibility of using PS for stable sensor device applications. This study provides a route for preparing highly sensitive organic vapour sensors with a precise selection of the fabrication parameters and demonstrating their prolonged performance.

  11. Satellite-derived sea surface height and sea surface wind data fusion for spilled oil tracking

    NASA Astrophysics Data System (ADS)

    Kozai, Katsutoshi

    2003-12-01

    An attempt is made to estimate the trajectory of the spilled oil from the sunken tanker Nakhodka occurred on January 2, 1997 in the Japan Sea by fusing two microwave sensor data, namely ERS-2 altimeter and ADEOS/NSCAT scatterometer data. In this study 'fusion' is defined as the method of more reliable prediction for the trajectory of spilled oil than before. Geostrophic current vectors are derived from ERS-2 altimeter and wind-induced drift vectors are derived from ADEOS/NSCAT scatterometer data These two different satellite-derived vectors are 'fused' together in the surface current model to estimate and evaluate the trajectory of spilled oil from the sunken tanker Nakhodka. The distribution of component of spill vector is mostly accounted for by the distribution of geostrophic velocity component during the study period with some discrepancies during March, 1997.

  12. Microstructure, Surface Characterization, and Electrochemical Behavior of New Ti-Zr-Ta-Ag Alloy in Simulated Human Electrolyte

    NASA Astrophysics Data System (ADS)

    Vasilescu, Cora; Drob, Silviu Iulian; Osiceanu, Petre; Moreno, Jose Maria Calderon; Prodana, Mariana; Ionita, Daniela; Demetrescu, Ioana; Marcu, Maria; Popovici, Ion Alexandru; Vasilescu, Ecaterina

    2017-01-01

    A new Ti-20Zr-5Ta-2Ag alloy was elaborated and characterized regarding its microstructure, its native passive film composition and thickness, its surface wettability, its electrochemical behavior in Ringer solution of different pH values, and its ion release. The new alloy has a bi-phase, α + β, acicular, homogeneous microstructure (scanning electron microscopy (SEM)). Its native passive film (12-nm thicknesses) consists of the protective TiO2, ZrO2, and Ta2O5 oxides, Ti and Ta suboxides, and metallic Ag (X-ray photoelectron spectroscopy (XPS) data). The alloy possesses high hydrophilic properties. The main electrochemical parameters of the new alloy are superior to those of Ti as a result of the beneficial influence of Zr, Ta, and Ag alloying elements, which reinforce its native passive film. Electrochemical impedance spectroscopy (EIS) spectra in Ringer solutions for the new alloy displayed better values of impedances and phase angles, proving a more insulate passive film than that on the Ti surface. The main corrosion parameters for the new Ti-20Zr-5Ta-2Ag alloy are more favorable by about 25 to 38 times than those of Ti, confirming extremely resistant passive film. The new Ti-20Zr-5Ta-2Ag alloy releases into Ringer solution low quantities of Ti4+, Zr4+ metallic ions (inductively coupled plasma-mass spectroscopy (ICP-MS)). The Ag+ ions are released in low quantity, conferring to this alloy's low antibacterial activity. All experimental results show that the new Ti-20Zr-5Ta-2Ag alloy fulfills the requirements for biocompatibility, corrosion resistance, and antibacterial protection.

  13. Polycyclic ferrocenyl(dihydro)thiazepine derivatives: Diastereo-selective synthesis, characterization, electrochemical behavior, theoretical and biological investigation.

    PubMed

    Sánchez García, Jessica J; Toledano-Magaña, Yanis; Flores-Alamo, Marcos; Martínez-Klimova, Elena; Galindo-Murillo, Rodrigo; Hernández-Ayala, Luis F; Ortiz-Frade, Luis; García-Ramos, Juan C; Klimova, Elena I

    2017-01-01

    The reaction of E-2-ferrocenylmethylidenetetralones and E,E-2,6-bis-(ferrocenylmethylidene)-cyclohexanone with 2-aminothiophenol proceed with high diastereoselectivity, forming the ~4.5:1 mixture of trans- and cis-isomers of polycyclic ferrocenylthiazepines, respectively. The reactions of E,E-2,5-bis-(ferrocenylmethylidene)cyclopentanone and E,E-3,5-bis-(ferrocenylmethylidene)-1-methyl-4-piperidone with 2-aminothiophenol take place stereo specifically to form the diastereomeric tricyclic thiazepines of cis- and trans-configuration, respectively. The structures of the obtained compounds were established by IR, (1)H and (13)C NMR spectroscopy and mass-spectrometry. The structures of the trans-tetralino[1,2a]-, trans-5,7-dimethyltetralino[1,2a]-2-ferrocenyl [1,5]benzo-2,3-dihydrothiazepines and cis-5-ferrocenyl-methylidenecyclopentano[1,2a]-2-ferrocenyl- [1,5]benzo-2,3-dihydrothiazepine were confirmed by X-ray diffraction analysis. An electrochemical study reveals that the diferrocenyl derivatives belong to a Class I compounds of the Robin-Day classification. This behavior is explained by the analysis of frontier orbitals as calculated by density functional theory, showing that only one ferrocenyl unit participates in the generation of HOMO and LUMO orbitals. Compounds 4a and 4c showed similar capacity to inhibit the proliferation of HM1: IMSS trophozoite cultures than the first choice drug for human amoebiasis treatment, metronidazole. Morphological changes induced in the trophozoites after drug exposure suggest a redox in balance as the probable mechanism of the parasite death.

  14. An original electrochemical method for assembling multilayers of terpyridine-based metallic complexes on a gold surface.

    PubMed

    Liatard, Sébastien; Chauvin, Jérôme; Balestro, Franck; Jouvenot, Damien; Loiseau, Frédérique; Deronzier, Alain

    2012-07-24

    A new method based on the electrochemical oxidation of thiols was used to easily generate multilayer assemblies of coordination complexes on a gold surface. For this purpose, two complexes bearing two anchoring groups for surface attachment have been prepared: [Ru(tpySH)(2)](2+) (1) and [Fe(tpySH)(2)](2+) (2) (tpySH = 4'-(2-(p-phenoxy)ethanethiol)-2,2':6',2″-terpyridine). Cyclic voltammetry of 1 in CH(3)CN exhibits two successive oxidation processes. The first is irreversible and attributed to the oxidation of the thiol substituents, whereas the second is reversible and corresponds to the 1 e(-) metal-centered oxidation. In the case of 2 both processes are superimposed. Monolayers of 1 or 2 have been formed on gold electrodes by spontaneous adsorption from micromolar solutions of the complexes in CH(3)CN. SAMs (self-assembled monolayers) exhibit redox behavior similar to the complexes in solution. The high surface coverage value obtained (Γ = 6 × 10(-10) and 4 × 10(-10) mol cm(-2) for 1 and 2, respectively) is consistent with a vertical orientation for the complexes; thus, one thiol is bound to the gold electrode, with the second unreacted thiol moiety exposed to the outer surface. Successive cyclic voltammetry induced a layer-by-layer nanostructural growth at the surface of the SAMs, and this is presumably due to the electrochemical formation of disulfide bonds, where the thiol moieties play a double role of both an anchoring group and an electroactive coupling agent. The conditions of the deposition are studied in detail. Modified electrodes containing both 1 and 2 alternatively can be easily prepared following this new approach. The film proved to be stable, displaying a similar current/voltage response for more than 10 repeating cycles in oxidation up to 0.97 V vs Ag/AgNO(3) (10(-2) M).

  15. In-situ electrochemically active surface area evaluation of an open-cathode polymer electrolyte membrane fuel cell stack

    NASA Astrophysics Data System (ADS)

    Torija, Sergio; Prieto-Sanchez, Laura; Ashton, Sean J.

    2016-09-01

    The ability to evaluate the electrochemically active surface area (ECSA) of fuel cell electrodes is crucial toward characterising designs and component suites in-situ, particularly when evaluating component durability in endurance testing, since it is a measure of the electrode area available to take part in the fuel cell reactions. Conventional methods to obtain the ECSA using cyclic voltammetry, however, rely on potentiostats that cannot be easily scaled to simultaneously evaluate all cells in a fuel cell stack of practical size, which is desirable in fuel cell development. In-situ diagnostics of an open-cathode fuel cell stack are furthermore challenging because the cells do not each possess an enclosed cathode compartment; instead, the cathodes are rather open to the environment. Here we report on a diagnostic setup that allows the electrochemically active surface area of each cell anode or cathode in an open-cathode fuel cell stack to be evaluated in-situ and simultaneously, with high resolution and reproducibility, using an easily scalable chronopotentiometry methodology and a gas-tight stack enclosure.

  16. Electrochemical properties of core-shell TiC-TiO2 nanoparticle films immobilized at ITO electrode surfaces.

    PubMed

    Stott, Susan J; Mortimer, Roger J; Dann, Sandie E; Oyama, Munetaka; Marken, Frank

    2006-12-14

    Titanium carbide (TiC) nanoparticles are readily deposited onto tin-doped indium oxide (ITO) electrodes in the form of thin porous films. The nanoparticle deposits are electrically highly conducting and electrochemically active. In aqueous media (at pH 7) and at applied potentials positive of 0.3 V vs. SCE partial anodic surface oxidation and formation (at least in part) of novel core-shell TiC-TiO2 nanoparticles is observed. Significant thermal oxidation of TiC nanoparticles by heating in air occurs at a temperature of 250 degrees C and leads first to core-shell TiC-TiO2 nanoparticles, next at ca. 350 degrees C to TiO2 (anatase), and finally at temperatures higher than 750 degrees C to TiO2 (rutile). Electrochemically and thermally partially oxidized TiC nanoparticles still remain very active and for some redox systems electrocatalytically active. Scanning and transmission electron microscopy (SEM and TEM), temperature dependent XRD, quartz crystal microbalance, and voltammetric measurements are reported. The electrocatalytic properties of the core-shell TiC-TiO2 nanoparticulate films are surveyed for the oxidation of hydroquinone, ascorbic acid, and dopamine in aqueous buffer media. In TiC-TiO2 core-shell nanoparticle films TiO2 surface reactivity can be combined with TiC conductivity.

  17. Influence of Surface Treatment on Magnetic Properties of Fe3O4 Nanoparticles Synthesized by Electrochemical Method.

    PubMed

    Marín, Tíffany; Montoya, Paula; Arnache, Oscar; Calderón, Jorge

    2016-07-14

    The changes of magnetic properties in magnetite nanoparticles during two different stabilization processes were investigated. Magnetic nanoparticles (MNPs) were obtained by electrochemical synthesis from two kinds of salts: (CH3)4NCl and NaCl. After that, two methods-steric and electrostatic-were used to stabilize MNPs with oleic acid (OA) and sodium hydroxide (NaOH), respectively. As a consequence, aqueous and organic dispersions were obtained after surface modification. The coated nanoparticles were characterized by TEM, zeta potential, thermogravimetry analysis (TGA), cyclic voltammetry (CV), magnetization measurements, and infrared and Mössbauer spectroscopy. The results showed that the particles were between 8 and 13 nm in size. In addition, the MNPs were coated with negative charge layers from NaOH by physisorption and coated with carboxylate groups from OA by the chemisorption process, and hence, they exhibited different reactivity and behavior depending on the nature of the electrolyte used in the electrochemical synthesis. Furthermore, the uncoated and coated MNPs had a narrow size distribution. Additionally, the saturation magnetization values showed dependence on the magnetite synthesis conditions and surface modifiers.

  18. Pratt & Whitney ESCORT derivative for mars surface power

    NASA Astrophysics Data System (ADS)

    Feller, Gerald J.; Joyner, Russell

    1999-01-01

    The purpose of this paper is to address the applicability of a common reactor system design from the Pratt & Whitney ESCORT nuclear thermal rocket engine concept to support current NASA mars surface-based power requirements. The ESCORT is a bimodal engine capable of supporting a wide range of propulsive thermal and vehicle electrical power requirements. The ESCORT engine is powered by a fast-spectrum beryllium-reflected CERMET-fueled nuclear reactor. In addition to an expander cycle propulsive mode, the ESCORT is capable of operating in an electrical power mode. In this mode, the reactor is used to heat a mixture of helium and xenon to drive a closed-loop Brayton cycle in order to generate electrical energy. Recent Design Reference Mission requirements (DRM) from NASA Johnson Space Center and NASA Lewis Research Center studies in 1997 and 1998 have detailed upgraded requirements for potential mars transfer missions. The current NASA DRM requires a nuclear thermal propulsion system capable of delivering total mission requirements of 200170 N (45000 lbf) thrust and 50 kWe of spacecraft electrical power. Additionally, these requirements detailed a surface power system capable of providing approximately 160 kW of electrical energy over an approximate 10 year period within a given weight and volume envelope. Current NASA studies use a SP-100 reactor (0.8 MT) and a NERVA derivative (1.6 MT) as baseline systems. A mobile power cart of approximate dimensions 1.7 m×4.5 m×4.4 m has been conceptualized to transport the reactor power system on the Mars Surface. The 63.25 cm diameter and 80.25 cm height of the ESCORT and its 1.3 MT of weight fit well within the current weight and volume target range of the NASA DRM requirements. The modifications required to the ESCORT reactor system to support this upgraded electrical power requirements along with operation in the Martian atmospheric conditions are addressed in this paper. Sufficient excess reactivity and burnup capability

  19. A Vs30-derived Near-surface Seismic Velocity Model

    NASA Astrophysics Data System (ADS)

    Ely, G. P.; Jordan, T. H.; Small, P.; Maechling, P. J.

    2010-12-01

    Shallow material properties, S-wave velocity in particular, strongly influence ground motions, so must be accurately characterized for ground-motion simulations. Available near-surface velocity information generally exceeds that which is accommodated by crustal velocity models, such as current versions of the SCEC Community Velocity Model (CVM-S4) or the Harvard model (CVM-H6). The elevation-referenced CVM-H voxel model introduces rasterization artifacts in the near-surface due to course sample spacing, and sample depth dependence on local topographic elevation. To address these issues, we propose a method to supplement crustal velocity models, in the upper few hundred meters, with a model derived from available maps of Vs30 (the average S-wave velocity down to 30 meters). The method is universally applicable to regions without direct measures of Vs30 by using Vs30 estimates from topographic slope (Wald, et al. 2007). In our current implementation for Southern California, the geology-based Vs30 map of Wills and Clahan (2006) is used within California, and topography-estimated Vs30 is used outside of California. Various formulations for S-wave velocity depth dependence, such as linear spline and polynomial interpolation, are evaluated against the following priorities: (a) capability to represent a wide range of soil and rock velocity profile types; (b) smooth transition to the crustal velocity model; (c) ability to reasonably handle poor spatial correlation of Vs30 and crustal velocity data; (d) simplicity and minimal parameterization; and (e) computational efficiency. The favored model includes cubic and square-root depth dependence, with the model extending to a depth of 350 meters. Model parameters are fit to Boore and Joyner's (1997) generic rock profile as well as CVM-4 soil profiles for the NEHRP soil classification types. P-wave velocity and density are derived from S-wave velocity by the scaling laws of Brocher (2005). Preliminary assessment of the new model

  20. Electrochemically active nanocrystalline SnO{sub 2} films: Surface modification with thiazine and oxazine dye aggregates

    SciTech Connect

    Liu, D.; Kamat, P.V.

    1995-03-01

    Thin films of SnO{sub 2}, nanocrystallites have been surface-modified with thionine, methylene blue, and oxazine 170 by adsorption from the corresponding dye solutions. The strong electrostatic interaction between the cationic dye and the negatively charged semiconductor nanocrystallites results in close packing of the dye on the semiconductor surface. These closely packed H-aggregates of the adsorbed dye are active both electrochemically and photoelectrochemically. Electron transfer from semiconductor nanocrystallites into the adsorbed dye aggregates leads to bleaching of the colored film. The extent of dye bleaching which is readily controlled by the applied potential, has been probed by spectroelectrochemical measurements. The photocurrent action spectra of these dye-modified SnO{sub 2} films indicate charge injection from excited dye aggregate into the semiconductor nanocrystallites with an incident photon-to-photocurrent efficiency of < 1 %.

  1. Facile in situ characterization of gold nanoparticles on electrode surfaces by electrochemical techniques: average size, number density and morphology determination.

    PubMed

    Wang, Ying; Laborda, Eduardo; Salter, Chris; Crossley, Alison; Compton, Richard G

    2012-10-21

    A fast and cheap in situ approach is presented for the characterization of gold nanoparticles from electrochemical experiments. The average size and number of nanoparticles deposited on a glassy carbon electrode are determined from the values of the total surface area and amount of gold obtained by lead underpotential deposition and by stripping of gold in hydrochloric acid solution, respectively. The morphology of the nanoparticle surface can also be analyzed from the "fingerprint" in lead deposition/stripping experiments. The method is tested through the study of gold nanoparticles deposited on a glassy carbon substrate by seed-mediated growth method which enables an easy control of the nanoparticle size. The procedure is also applied to the characterization of supplied gold nanoparticles. The results are in satisfactory agreement with those obtained via scanning electron microscopy.

  2. In situ Wilhelmy balance surface energy determination of poly(3-hexylthiophene) and poly(3,4-ethylenedioxythiophene) during electrochemical doping-dedoping.

    PubMed

    Wang, Xiangjun; Ederth, Thomas; Inganäs, Olle

    2006-10-24

    Changes in the contact angle between conjugated polymers surface poly(3-hexylthiophene) [P3HT] and poly(3,4-ethylenedioxythiophene) (PEDOT) upon electrochemical doping-dedoping in aqueous electrolyte were determined in situ using a Wilhelmy plate tensiometer in an electrochemical cell. The hydrophobic P3HT was less hydrophobic in the oxidized state than in the neutral state; the more hydrophilic PEDOT was less hydrophilic in the oxidized state than when neutral. The tensiometry results were in good agreement with those measured by contact angle goniometry, and further corroborated by the capillary rise upon doping in a fluid cell with two parallel polymer coated plates, another in situ dynamic determination method. The contact angle changes depend on doping potential, electrolyte type, and concentration. We also deconvoluted the surface energy into components of van der Waals and acid-base interactions, using three probe liquids on the polymer surfaces, ex situ the electrochemical cell. The methods and the obtained results are relevant for the science and technology areas of printed electronics and electrochemical devices and for the understanding of surface energy modification by electrochemical doping.

  3. The effect of surface treatment on the surface texture and contact angle of electrochemically deposited hydroxyapatite coating and on its interaction with bone-forming cells.

    PubMed

    Eliaz, Noam; Shmueli, Sharon; Shur, Irena; Benayahu, Dafna; Aronov, Daniel; Rosenman, Gil

    2009-10-01

    This work demonstrates the effects of both surface preparation and surface post-treatment by exposure to electron beam on the surface texture, contact angle and the interaction with bone-forming cells of electrochemically deposited hydroxyapatite (HAp) coating. Both the surface texture and the contact angle of the ground titanium substrate changed as a result of either heat treatment following soaking in NaOH solution or soaking in H(2)O(2) solution. Consequently, the shape of the current transients during potentiostatic deposition of HAp changed, and the resulting coatings exhibited different surface textures and contact angles. The developed interfacial area ratio Sdr and the core fluid retention index Sci were found more reliable than the mean roughness R(a) and the root-mean-square roughness Z(rms) in correlating the adhesion of the coating to the metal substrate and the cellular response with surface texture. The NaOH pretreatment provided the highest surface area and induced the highest cell attachment, even though the H(2)O(2) treatment provided the highest hydrophilicity to the metal substrate. Electrodeposition at pH 6 was found preferable compared to electrodeposition at pH 4.2. The ability to modify the cellular response by exposure to unique electron-beam surface treatment was demonstrated. The very high hydrophilicity of the as-deposited HAp coating enhanced its bioactivity.

  4. Versatile aptasensor for electrochemical quantification of cell surface glycan and naked-eye tracking glycolytic inhibition in living cells.

    PubMed

    Zhang, Jing-Jing; Cheng, Fang-Fang; Zheng, Ting-Ting; Zhu, Jun-Jie

    2017-03-15

    Quantifying the glycan expression status on cell surfaces is of vital importance for insight into the glycan function in biological processes and related diseases. Here we developed a versatile aptasensor for electrochemical quantification of cell surface glycan by taking advantage of the cell-specific aptamer, and the lectin-functionalized gold nanoparticles acting as both a glycan recognition unit and a signal amplification probe. To construct the aptasensor, amine-functionalized mucin 1 protein (MUC1) aptamer was first covalently conjugated to carboxylated-magnetic beads (MBs) using the succinimide coupling (EDC-NHS) method. On the basis of the specific recognition between aptamer and MUC1 protein that overexpressed on the surface of MCF-7 cells, the aptamer conjugated MBs showed a predominant capability for cell capture with high selectivity. Moreover, a lectin-based nanoprobe was designed by noncovalent assembly of concanavalin A (ConA) on gold nanoparticles (AuNPs). This nanoprobe incorporated the abilities of both the specific carbohydrate recognition and the signal amplification based on the gold-promoted reduction of silver ions. By coupling with electrochemical stripping analysis, the proposed sandwich-type cytosensor showed an excellent analytical performance for the ultrasensitive detection of MCF-7 cells and quantification of cell surface glycan. More importantly, taking advantage of Con A-gold nanoprobe catalyzed silver enhancement, the proposed method was further used for naked-eye tracking glycolytic inhibition in living cells. This aptasensor holds great promise as a new point-of-care diagnostic tool for analyzing glycan expression on living cells and further helps cancer diagnosis and treatment.

  5. Effects of Microstructure on Electrode Properties of Nanosheet-Derived Hx(Ni1/3Co1/3Mn1/3)O2 for Electrochemical Capacitors

    PubMed Central

    Yano, Masato; Suzuki, Shinya; Miyayama, Masaru; Ohgaki, Masataka

    2013-01-01

    Nanosheet-derived Hx(Ni1/3Co1/3Mn1/3)O2 was prepared by restacking (Ni1/3Co1/3Mn1/3)O2 nanosheets with large or small lateral sizes and their electrochemical properties in a 1 M KOH aqueous solution; microstructural factors were compared with those of bulk Hx(Ni1/3Co1/3Mn1/3)O2 (HNCM). The electrodes composed of small nanosheets exhibited very large capacitances of 1241 F·g−1 (395 mAh·g−1) at a current density of 50 mA·g−1, and 430 F·g−1 (100 mAh·g−1) at a large current density of 1000 mA·g−1. These large capacitances resulted from a heterogeneous layer structure with a large surface area and pore volume. The electrodes of large nanosheets, with a strongly interconnected microstructure and a surface area slightly larger than that of HNCM, exhibited good cycle stability and capacitances larger than that of HNCM. Microstructural control through the restacking of (Ni1/3Co1/3Mn1/3)O2 nanosheets improved the electrochemical properties of Hx(Ni, Co, Mn)O2.

  6. Microscopically derived potential energy surfaces from mostly structural considerations

    SciTech Connect

    Ermamatov, M.J.; Hess, Peter O.

    2016-08-15

    A simple procedure to estimate the quadrupole Potential-Energy-Surface (PES) is presented, using mainly structural information, namely the content of the shell model space and the Pauli exclusion principle. Further microscopic properties are implicitly contained through the use of results from the Möller and Nix tables or experimental information. A mapping to the geometric potential is performed yielding the PES. The General Collective Model is used in order to obtain an estimate on the spectrum and quadrupole transitions, adjusting only the mass parameter. First, we test the conjecture on known nuclei, deriving the PES and compare them to known data. We will see that the PES approximates very well the structure expected. Having acquired a certain confidence, we predict the PES of several chain of isotopes of heavy and super-heavy nuclei and at the end we investigate the structure of nuclei in the supposed island of stability. One of the main points to show is that simple assumptions can provide already important information on the structure of nuclei outside known regions and that spectra and electromagnetic transitions can be estimated without using involved calculations and assumptions. The procedure does not allow to calculate binding energies. The method presented can be viewed as a starting point for further improvements.

  7. Surface-enhanced Raman scattering-active Au/TiO{sub 2} films prepared by electrochemical and photochemical methods

    SciTech Connect

    Yang, Kuang-Hsuan; Chang, Chia-Ming

    2013-02-15

    Graphical abstract: In the presence of TiO{sub 2} NPs before the ORCs the optimal wavelength of UV light resulting in the strongest SERS effect being 310 nm. Display Omitted Highlights: ► SERS-active Au/TiO{sub 2} prepared by electrochemical and photochemical methods. ► UV light of 310 nm is suitable for obtaining Au/TiO{sub 2} with strong SERS effect. ► Presence of TiO{sub 2} before ORCs is responsible for obtaining SERS-active Au/TiO{sub 2}. -- Abstract: In this work, we report a new strategy for the preparation of surface-enhanced Raman scattering (SERS)-active Au/TiO{sub 2}(P25) nanocomposites (NCs), using electrochemical and photochemical methods. First, Au substrates were subjected to electrochemical oxidation–reduction cycles (ORCs) in a deoxygenated aqueous solution containing 0.1 M HCl and 1 mM TiO{sub 2}. After the ORC treatment AuCl{sub 4}{sup −}-adsorbed TiO{sub 2} complexes were produced in the solution. These complex-containing substrates were then irradiated with UV light at 310 nm to synthesize Au/TiO{sub 2} NCs with strong SERS activities for probe molecules of rhodamine 6G (R6G) and conductive polymers of polypyrrole (PPy). Experimental results indicated that the wavelength of UV light and the presence of TiO{sub 2} before and after the ORC procedure during the preparation process both affected the resulting SERS activities.

  8. Influence of crystallite size and surface morphology on electrochemical properties of annealed TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Munirathinam, Balakrishnan; Pydimukkala, Haveela; Ramaswamy, Narayanan; Neelakantan, Lakshman

    2015-11-01

    The current study investigates the effect of crystallite size and surface morphology of TiO2 nanotubes on their wettability and electrochemical properties. Self-organized amorphous TiO2 nanotubes were synthesized by anodization process in an acidic (0.5 wt% HF) and a neutral electrolyte (1 M Na2SO4 + 0.5 wt% NaF). Subsequently, the nanotubes were annealed at 450 °C to achieve crystalline phase. Scanning electron microscope micrographs revealed that nanotubes formed from the neutral bath are four times longer (1.2 μm) than the ones synthesized from the acidic bath (325 nm). The charge consumed during anodization is greater under the acidic conditions implying the severity of the attack on the nanotubes by the electrolyte. X-Ray diffraction analysis showed that after annealing TiO2 crystallizes in the tetragonal lattice as anatase structure. Peak fitting method for line profile analysis was employed to estimate the crystallite size and the micro strain. The oxide nanotubes formed in neutral medium showed smaller crystallite size (28.91 nm) than the one formed in acidic medium (43.37 nm). Wettability measurements showed wetting angles <60°, indicating hydrophilic nature of the anatase nanotubes. Further, both the dimensional aspect (i.e., length and diameter of nanotubes) and the crystallite size have significant effect on the hydrophilic behavior. Electrochemical impedance spectroscopy in a simulated body fluid environment confirmed that structural changes in the oxide layer influence the electrochemical properties. Polarization studies demonstrated that crystallite size affects the passive behavior of the nanotubes. Smaller crystallite size (28.91 nm) lowers the passive current density (0.11 μA cm-2), indicating the good protectiveness.

  9. Derivation of GNSS derived station velocities for a surface deformation model in the Austrian region

    NASA Astrophysics Data System (ADS)

    Umnig, Elke; Weber, Robert; Maras, Jadre; Brückl, Ewald

    2016-04-01

    This contribution deals with the first comprehensive analysis of GNSS derived surface velocities computed within an observation network of about 100 stations covering the whole Austrian territory and parts of the neighbouring countries. Coordinate time series are available now, spanning a period of 5 years (2010.0-2015.0) for one focus area in East Austria and one and a half year (2013.5-2015.0) for the remaining part of the tracking network. In principle the data series are stemming from two different GNSS campaigns. The former was set up to investigate intra plate tectonic movements within the framework of the project ALPAACT (seismological and geodetic monitoring of ALpine-PAnnonian ACtive Tectonics), the latter was designed to support a number of various requests, e.g. derivation of GNSS derived water vapour fields, but also to expand the foresaid tectonic studies. In addition the activities within the ALPAACT project supplement the educational initiative SHOOLS & QUAKES, where scholars contribute to seismological research. For the whole period of the processed coordinate time series daily solutions have been computed by means of the Bernese software. The processed coordinate time series are tied to the global reference frame ITRF2000 as well as to the frame ITRF2008. Due to the transition of the reference from ITRF2000 to ITRF2008 within the processing period, but also due to updates of the Bernese software from version 5.0 to 5.2 the time series were initially not fully consistent and have to be re-aligned to a common frame. So the goal of this investigation is to derive a nationwide consistent horizontal motion field on base of GNSS reference station data within the ITRF2008 frame, but also with respect to the Eurasian plate. In this presentation we focus on the set-up of the coordinate time series and on the problem of frame alignment. Special attention is also paid to the separation into linear and periodic motion signals, originating from tectonic or non

  10. Investigation of the electrochemically active surface area and lithium diffusion in graphite anodes by a novel OsO4 staining method

    NASA Astrophysics Data System (ADS)

    Pfaffmann, Lukas; Birkenmaier, Claudia; Müller, Marcus; Bauer, Werner; Mitsch, Tim; Feinauer, Julian; Krämer, Yvonne; Scheiba, Frieder; Hintennach, Andreas; Schleid, Thomas; Schmidt, Volker; Ehrenberg, Helmut

    2016-03-01

    Negative electrodes of lithium-ion batteries generally consist of graphite-based active materials. In order to realize batteries with a high current density and therefore accelerated charging processes, the intercalation of lithium and the diffusion processes of these carbonaceous materials must be understood. In this paper, we visualized the electrochemical active surface area for three different anode materials using a novel OsO4 staining method in combination with scanning electron microscopy techniques. The diffusion behavior of these three anode materials is investigated by potentiostatic intermittent titration technique measurements. From those we determine the diffusion coefficient with and without consideration of the electrochemical active surface area.

  11. p-Si(1 1 1):H/ionic liquid interface investigated through a combination of electrochemical measurements and reflection high energy electron diffraction surface analysis in vacuum

    NASA Astrophysics Data System (ADS)

    Watanabe, Ko; Maruyama, Shingo; Matsumoto, Yuji

    2016-07-01

    A combination study of electrochemical measurements and reflection high energy electron diffraction (RHEED) surface analysis experiments in a vacuum was first demonstrated to characterize a p-Si(1 1 1):H/ionic liquid interface. Mott-Schottky plot analysis was made to successfully not only evaluate the acceptor density and flat band potential of the p-Si(1 1 1):H, but also get some insight into its surface states. Furthermore, the electric double layer capacitance and specific adsorption properties at the IL/Si(1 1 1):H interface as well as the electrochemical interface stability will be discussed in this paper.

  12. Electrochemical Epitaxy

    DTIC Science & Technology

    1994-06-25

    formation. Frequently, the first atmic layer of the depositing element forms at a potential prior to, under, that needed to deposit the bulk element. Thiis...ps referred to as undepotential deposition (UPD). UPD is an importaM well studied and reviewed area of electrochemical surface science [4-6]. In...general, UPD results in deposits one atom thick (an atomic layer), although the absolute coveage is fequmty some function of the deposition potential. In

  13. Electrochemical characterization of surface complexes formed on Cu and Ta in succinic acid based solutions used for chemical mechanical planarization

    NASA Astrophysics Data System (ADS)

    Sulyma, Christopher M.; Roy, Dipankar

    2010-02-01

    Open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H 2O 2, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta. The data analysis steps are discussed in detail to demonstrate how the D.C. and A.C. electrochemical probes can be combined in the framework of the RDE technique to design and test CMP slurry solutions.

  14. Enhanced electrochemical performance of Si-Cu-Ti thin films by surface covered with Cu3Si nanowires

    NASA Astrophysics Data System (ADS)

    Xu, Kaiqi; He, Yu; Ben, Liubin; Li, Hong; Huang, Xuejie

    2015-05-01

    Si-Cu-Ti thin films with Cu3Si nanowires on the surface and voids in the Cu layer are fabricated for the first time by magnetron sputtering combined with atomic layer deposition (ALD) of alumina. The formation of the surface Cu3Si nanowires is strongly dependent on the thickness of the coated alumina and cooling rate of the thin films during annealing. The maximum coverage of the surface Cu3Si nanowires is obtained with an alumina thickness of 2 nm and a cooling rate of 1 °C min-1. The electrode based on this thin film shows an excellent capacity retention of more than 900 mAh g-1 and a high columbic efficiency of more than 99% after 100 cycles. The improvement of the electrochemical performance of Si-Cu-Ti thin film electrode is attributed to the surface Cu3Si nanowires which reduce the polarization and inhomogeneous lithiation by formation of a surface conductive network, in addition to the alleviation of volume expansion of Si by voids in the Cu layer during cycling.

  15. Surface-Electronic-State-Modulated, Single-Crystalline (001) TiO2 Nanosheets for Sensitive Electrochemical Sensing of Heavy-Metal Ions.

    PubMed

    Zhou, Wen-Yi; Liu, Jin-Yun; Song, Jie-Yao; Li, Jin-Jin; Liu, Jin-Huai; Huang, Xing-Jiu

    2017-03-21

    Intrinsically low conductivity and poor reactivity restrict many semiconductors from electrochemical detection. Usually, metal- and carbon-based modifications of semiconductors are necessary, making them complex, expensive, and unstable. Here, for the first time, we present a surface-electronic-state-modulation-based concept applied to semiconductors. This concept enables pure semiconductors to be directly available for ultrasensitive electrochemical detection of heavy-metal ions without any modifications. As an example, a defective single-crystalline (001) TiO2 nanosheet exhibits high electrochemical performance toward Hg(II), including a sensitivity of 270.83 μA μM(-1) cm(-2) and a detection limit of 0.017 μM, which is lower than the safety standard (0.03 μM) of drinking water established by the World Health Organization (WHO). It has been confirmed that the surface oxygen vacancy adsorbs an O2 molecule while the Ti(3+) donates an electron, forming the O2(•-) species that facilitate adsorption of Hg(II) and serve as active sites for electron transfer. These findings not only extend the electrochemical sensing applications of pure semiconductors but also stimulate new opportunities for investigating atom-level electrochemical behaviors of semiconductors by surface electronic-state modulation.

  16. Satellite-derived sea surface height and sea surface wind data fusion for spilled oil tracking

    NASA Astrophysics Data System (ADS)

    Kozai, K.

    Data fusion is defined as a framework with the purpose of obtaining information of 'greater quality'. Within the framework tools are expressed for the alliance of data originating from different sources. The exact definition of 'greater quality' is stated in this context as more reliable prediction for the trajectory of spilled oil from two different microwave sensor data, namely ERS-2 altimeter and ADEOS/NSCAT scatterometer data. An example is presented in the case of trajectory of bow section and associated oil upwelling from the sunken tanker Nakhodka occurred from January to June in 1997 in Japan Sea. Spill distance is defined as a horizontal distance from the oil upwelling point to the location of sunken Nakhodka and a spill direction is defined as an angle made by the geographic north and the line corresponding to the spill distance. Geostrophic current vectors are derived from ERS-2 altimeter and wind-induced current vectors are derived from ADEOS/NSCAT scatterometer data. These two different satellite-derived vectors are 'fused' together in the surface current model to estimate and evaluate the trajectory of bow section and associated oil upwelling from the sunken tanker Nakhodka. Result of comparison between the estimated and the observed trajectory of bow section indicates that the estimated trajectory is agreed well with the observed one in the first half of drift period, while in the latter half of drift period the estimated trajectory is not agreed well with the observed one, which may be attributable to changes of wind directions within 24 hours from the satellite overpasses. Moreover the comparison between spill vector and 'fused' surface current vector shows the good correspondence in terms of direction when in situ wind accelerates the surface current vector, while the comparison between the twos shows the bad correspondence when the temporal changes of wind vector occurs.

  17. Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2

    DOE PAGES

    Hod, Idan; Sampson, Matthew D.; Deria, Pravas; ...

    2015-09-18

    Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (~1015 sites/cm2). The chemical products of the reduction, obtained with ~100% Faradaic efficiency, aremore » mixtures of CO and H2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.« less

  18. Electrochemical deposition of conducting polymer coatings on magnesium surfaces in ionic liquid

    PubMed Central

    Luo, Xiliang; Cui, Xinyan Tracy

    2012-01-01

    A conducting polymer based smart coating for magnesium (Mg) implants that can both improve the corrosion resistance of Mg and release drug in a controllable way is reported. As the ionic liquid is a highly conductive and stable solvent with a very wide electrochemical window, the conducting polymer coatings can be directly electrodeposited on the active metal Mg in ionic liquid at mild conditions, and Mg is considerably stable during the electrodeposition. The electrodeposited Poly(3,4-ethylenedioxythiophene) (PEDOT) coatings on Mg are uniform and can significantly improve the corrosion resistance of Mg. In addition, the PEDOT coatings can load the anti-inflammatory drug dexamethasone during the electrodeposition which can be subsequently released upon electric stimulation. PMID:20832505

  19. Synthesis of trimethoprim metal complexes: Spectral, electrochemical, thermal, DNA-binding and surface morphology studies.

    PubMed

    Demirezen, Nihat; Tarınç, Derya; Polat, Duygu; Ceşme, Mustafa; Gölcü, Ayşegül; Tümer, Mehmet

    2012-08-01

    Complexes of trimethoprim (TMP), with Cu(II), Zn(II), Pt(II), Ru(III) and Fe(III) have been synthesized. Then, these complexes have been characterized by spectroscopic techniques involving UV-vis, IR, mass and (1)H NMR. CHN elemental analysis, electrochemical and thermal behavior of complexes have also been investigated. The electrochemical properties of all complexes have been investigated by cyclic voltammetry (CV) using glassy carbon electrode. The biological activity of the complexes has been evaluated by examining their ability to bind to calf-thymus DNA (CT DNA) with UV spectroscopy and cyclic voltammetry. UV studies of the interaction of the complexes with DNA have shown that these compounds can bind to CT DNA. The binding constants of the complexes with CT DNA have also been calculated. The cyclic voltammograms of the complexes in the presence of CT DNA have shown that the complexes can bind to CT DNA by both the intercalative and the electrostatic binding mode. The antimicrobial activity of these complexes has been evaluated against three Gram-positive and four Gram-negative bacteria. Antifungal activity against two different fungi has been evaluated and compared with the reference drug TMP. Almost all types of complexes show excellent activity against all type of bacteria and fungi. The morphology of the CT DNA, TMP, metal ions and metal complexes has been investigated by scanning electron microscopy (SEM). To get the SEM images, the interaction of compounds with CT DNA has been studied by means of differential pulse voltammetry (DPV) at CT DNA modified pencil graphite electrode (PGE). The decrease in intensity of the guanine oxidation signals has been used as an indicator for the interaction mechanism.

  20. Synthesis of trimethoprim metal complexes: Spectral, electrochemical, thermal, DNA-binding and surface morphology studies

    NASA Astrophysics Data System (ADS)

    Demirezen, Nihat; Tarınç, Derya; Polat, Duygu; Çeşme, Mustafa; Gölcü, Ayşegül; Tümer, Mehmet

    Complexes of trimethoprim (TMP), with Cu(II), Zn(II), Pt(II), Ru(III) and Fe(III) have been synthesized. Then, these complexes have been characterized by spectroscopic techniques involving UV-vis, IR, mass and 1H NMR. CHN elemental analysis, electrochemical and thermal behavior of complexes have also been investigated. The electrochemical properties of all complexes have been investigated by cyclic voltammetry (CV) using glassy carbon electrode. The biological activity of the complexes has been evaluated by examining their ability to bind to calf-thymus DNA (CT DNA) with UV spectroscopy and cyclic voltammetry. UV studies of the interaction of the complexes with DNA have shown that these compounds can bind to CT DNA. The binding constants of the complexes with CT DNA have also been calculated. The cyclic voltammograms of the complexes in the presence of CT DNA have shown that the complexes can bind to CT DNA by both the intercalative and the electrostatic binding mode. The antimicrobial activity of these complexes has been evaluated against three Gram-positive and four Gram-negative bacteria. Antifungal activity against two different fungi has been evaluated and compared with the reference drug TMP. Almost all types of complexes show excellent activity against all type of bacteria and fungi. The morphology of the CT DNA, TMP, metal ions and metal complexes has been investigated by scanning electron microscopy (SEM). To get the SEM images, the interaction of compounds with CT DNA has been studied by means of differential pulse voltammetry (DPV) at CT DNA modified pencil graphite electrode (PGE). The decrease in intensity of the guanine oxidation signals has been used as an indicator for the interaction mechanism.

  1. A novel electrochemical sensor surface for the detection of hydrogen peroxide using cyclic bisureas/gold nanoparticle composite.

    PubMed

    Mathew, Manjusha; Sandhyarani, N

    2011-10-15

    A novel electrochemical sensor surface with enhanced sensitivity for the detection of hydrogen peroxide has been developed based on the layer-by-layer assembly of mercapto propionic acid (MPA), cystine-based polymethylene-bridged cyclic bisureas (CBU)/gold nanoparticle (AuNP) and horseradish peroxidase (HRP) on gold electrode. Possibility of a large number of hydrogen bonds, allowed by the chemical and sterical structure of the CBU ensures the proper immobilization of the enzyme in favorable orientation and retention of enzymatic activity. Efficient electron tunneling property of AuNP together with its electrocatalytic activity leads to higher sensitivity in the detection of H(2)O(2). In cyclic voltammetry measurements a cathodic current due to direct electron transfer of HRP is observed which, indicates excellent electrocatalytic activity of the sensor surface. The biosensor surface modified with gold nanoparticle and CBU showed a lower detection limit of 50 nM for hydrogen peroxide. Chronoamperometry is performed at -0.3 V and Michaelis-Menten constant K(M)(app) value is estimated to be 4.5 μM. The newly developed sensor surface showed very high stability, reproducibility and high sensitivity.

  2. Electrochemical impedance spectroscopy and surface plasmon resonance studies of DNA hybridization on gold/SiOx interfaces.

    PubMed

    Manesse, Maël; Stambouli, Valerie; Boukherroub, Rabah; Szunerits, Sabine

    2008-08-01

    The use of Au/SiO(x) interfaces for the investigation of DNA hybridization using electrochemical impedance spectroscopy (EIS) and surface plasmon resonance (SPR) simultaneously is demonstrated. Standard glass chemistry was used to link single-stranded DNA (ss-DNA) on aldehyde-terminated Au/SiO(x) interfaces. The layer thickness and amount of grafted oligonucleotides (ODNs) were calculated from SPR on the basis of a multilayer system of glass/Ti/Au/SiO(x)/grafted molecule. Capacitance and resistance values of the modified interface before and after hybridization were calculated from EIS data using an equivalent circuit and allowed the affinity rate constant, K(A) = 4.07 x 10(5) M(-1), to be determined. The EIS results were comparable to those obtained by SPR hybridization kinetics recorded in parallel.

  3. Identical Location Transmission Electron Microscopy Imaging of Site-Selective Pt Nanocatalysts: Electrochemical Activation and Surface Disordering.

    PubMed

    Arán-Ais, Rosa M; Yu, Yingchao; Hovden, Robert; Solla-Gullón, Jose; Herrero, Enrique; Feliu, Juan M; Abruña, Héctor D

    2015-12-02

    We have employed identical location transmission electron microscopy (IL-TEM) to study changes in the shape and morphology of faceted Pt nanoparticles as a result of electrochemical cycling; a procedure typically employed for activating platinum surfaces. We find that the shape and morphology of the as-prepared hexagonal nanoparticles are rapidly degraded as a result of potential cycling up to +1.3 V. As few as 25 potential cycles are sufficient to cause significant degradation, and after about 500-1000 cycles the particles are dramatically degraded. We also see clear evidence of particle migration during potential cycling. These finding suggest that great care must be exercised in the use and study of shaped Pt nanoparticles (and related systems) as electrocatlysts, especially for the oxygen reduction reaction where high positive potentials are typically employed.

  4. Role of electronic, geometric, and surface properties on the mechanism of the electrochemical hydriding/dehydriding reactions

    SciTech Connect

    Srinivasan, S.; Zhang, W.; Kumar, M.P.S.

    1996-03-01

    Since 1990 there has been an ongoing collaboration among the authors to investigate the role of individual elements on the thermodynamics and kinetics of hydriding/dehydriding reactions. This review article presents the electrochemical and physicochemical characteristics of hydriding/dehydriding reactions from the point of view of their dependence on electronic, geometric and surface properties of the hydride materials. X-ray absorption spectroscopy (XAS), x-ray diffraction spectroscopy (XRD) and scanning vibrating electrode technique (SVET) studies were based on AB{sub 5} type alloys, partially substituted by other elements. Expansion of the unit cell volume and a larger Ni d band vacancy are beneficial for increasing the amount of the hydrogen storage. XAS and SVET showed that the Ce substitution for La in an AB{sub 5} alloy enhances the lifetime of hydride electrode.

  5. Metrological characteristics of the flat voltammetric electrode in time domain with a reversible electrochemical reaction running on the surface

    NASA Astrophysics Data System (ADS)

    Suchocki, Krzysztof

    2016-11-01

    The study deals with metrological characteristics of the flat voltammetric electrode used for determination of ions concentration by the DC voltammetric method, where a reversible reaction of electrochemical oxidation/reduction takes place on the surface. The analysis shows that such voltammetric electrode acts as a transducer of the first order, where the input signal is a concentration of marked ions in tested solution and the output signal is the current associated with a reversible reaction of oxidation / reduction. Metrological characteristics of such electrode in the time domain are determined by its sensitivity and time constant. The values of these parameters are defined by measurements of characteristics of the voltammetric electrode, polarization voltage and marked ions. To determine the effect of a particular volume of each of these parameters several numerical simulations are presented.

  6. Characterization of Surface Film Growth During Electrochemical Process: Nickel/Nickel Alloys in Seawater

    DTIC Science & Technology

    2006-11-01

    interacts with the specimen, causing the material to emit electrons with an energy that is characteristic of the atoms from which they were emitted...surface and within several atomic layers of the surface. The surface sensitivity of the XPS method arises from its ability to measure the energy of...Therefore, the emitted electrons represent elements present in the outer layer or several atomic layers below the surface. The concentration of a given

  7. Growth of rutile TiO₂ on the convex surface of nanocylinders: from nanoneedles to nanorods and their electrochemical properties.

    PubMed

    Kong, Junhua; Wei, Yuefan; Zhao, Chenyang; Toh, Meng Yew; Yee, Wu Aik; Zhou, Dan; Phua, Si Lei; Dong, Yuliang; Lu, Xuehong

    2014-04-21

    In this work, bundles of rutile TiO₂ nanoneedles/nanorods are hydrothermally grown on carbon nanofibers (CNFs), forming free-standing mats consisting of three dimensional hierarchical nanostructures (TiO₂-on-CNFs). Morphologies and structures of the TiO₂-on-CNFs are studied using a field-emission scanning electron microscope (FESEM), transmission electron microscope (TEM), X-ray diffractometer (XRD) and thermogravimetric analyzer (TGA). Their electrochemical properties as electrodes in lithium ion batteries (LIBs) are investigated and correlated with the morphologies and structures. It is shown that the lateral size of the TiO₂ nanoneedles/nanorods ranges from a few nanometers to tens of nanometers, and increases with the hydrothermal temperature. Small interspaces are observed between individual nanoneedles/nanorods, which are due to the diverging arrangement of nanoneedles/nanorods induced by growing on the convex surface of nanocylinders. It is found that the growth process can be divided into two stages: initial growth on the CNF surface and further growth upon re-nucleation on the TiO₂ bundles formed in the initial growth stage. In order to achieve good electrochemical performance in LIBs, the size of the TiO₂ nanostructures needs to be small enough to ensure complete alloying and fast charge transport, while the further growth stage has to be avoided to realize direct attachment of TiO₂ nanostructures on the CNFs, facilitating electron transport. The sample obtained after hydrothermal treatment at 130 °C for 2 h (TiO₂-130-2) shows the above features and hence exhibits the best cyclability and rate capacity among all samples; the cyclability and rate capacity of TiO₂-130-2 are also superior to those of other rutile TiO₂-based LIB electrodes.

  8. Derivative Form of Off-axis Aberration Correction Surface and Its Application in Solar Energy Concentration

    NASA Astrophysics Data System (ADS)

    Li, Li; Chen, Ying-Tian; Hu, Sen

    2009-02-01

    By using the derivative method, we obtained the same result with that of the previous work of Chen et al. in 2006. Different from the integral form, the derivative form of the surface expression published in this paper is derived from differential equation and based on the theory of non-imaging focusing heliostat proposed by Chen et al. in 2001. The comparison of the derivative form of fixed aberration correction surface has been made with that of integral form surface as well as that of spherical surface in concentrating the solar ray.

  9. Comparison of diffusivity data derived from electrochemical and NMR investigations of the SeCN¯/(SeCN)2/(SeCN)3¯ system in ionic liquids.

    PubMed

    Solangi, Amber; Bond, Alan M; Burgar, Iko; Hollenkamp, Anthony F; Horne, Michael D; Rüther, Thomas; Zhao, Chuan

    2011-06-02

    Electrochemical studies in room temperature ionic liquids are often hampered by their relatively high viscosity. However, in some circumstances, fast exchange between participating electroactive species has provided beneficial enhancement of charge transport. The iodide (I¯)/iodine (I(2))/triiodide (I(3)¯) redox system that introduces exchange via the I¯ + I(2) ⇌ I(3)¯ process is a well documented example because it is used as a redox mediator in dye-sensitized solar cells. To provide enhanced understanding of ion movement in RTIL media, a combined electrochemical and NMR study of diffusion in the {SeCN¯-(SeCN)(2)-(SeCN)(3)¯} system has been undertaken in a selection of commonly used RTILs. In this system, each of the Se, C and N nuclei is NMR active. The electrochemical behavior of the pure ionic liquid, [C(4)mim][SeCN], which is synthesized and characterized here for the first time, also has been investigated. Voltammetric studies, which yield readily interpreted diffusion-limited responses under steady-state conditions by means of a Random Assembly of Microdisks (RAM) microelectrode array, have been used to measure electrochemically based diffusion coefficients, while self-diffusion coefficients were measured by pulsed field gradient NMR methods. The diffusivity data, derived from concentration and field gradients respectively, are in good agreement. The NMR data reveal that exchange processes occur between selenocyanate species, but the voltammetric data show the rates of exchange are too slow to enhance charge transfer. Thus, a comparison of the iodide and selenocyanate systems is somewhat paradoxical in that while the latter give RTILs of low viscosity, sluggish exchange kinetics prevent any significant enhancement of charge transfer through direct electron exchange. In contrast, faster exchange between iodide and its oxidation products leads to substantial electron exchange but this effect does not compensate sufficiently for mass transport

  10. Effects of Nanowire Length and Surface Roughness on the Electrochemical Sensor Properties of Nafion-Free, Vertically Aligned Pt Nanowire Array Electrodes.

    PubMed

    Li, Zhiyang; Leung, Calvin; Gao, Fan; Gu, Zhiyong

    2015-09-04

    In this paper, vertically aligned Pt nanowire arrays (PtNWA) with different lengths and surface roughnesses were fabricated and their electrochemical performance toward hydrogen peroxide (H₂O₂) detection was studied. The nanowire arrays were synthesized by electroplating Pt in nanopores of anodic aluminum oxide (AAO) template. Different parameters, such as current density and deposition time, were precisely controlled to synthesize nanowires with different surface roughnesses and various lengths from 3 μm to 12 μm. The PtNWA electrodes showed better performance than the conventional electrodes modified by Pt nanowires randomly dispersed on the electrode surface. The results indicate that both the length and surface roughness can affect the sensing performance of vertically aligned Pt nanowire array electrodes. Generally, longer nanowires with rougher surfaces showed better electrochemical sensing performance. The 12 μm rough surface PtNWA presented the largest sensitivity (654 μA·mM⁻¹·cm⁻²) among all the nanowires studied, and showed a limit of detection of 2.4 μM. The 12 μm rough surface PtNWA electrode also showed good anti-interference property from chemicals that are typically present in the biological samples such as ascorbic, uric acid, citric acid, and glucose. The sensing performance in real samples (river water) was tested and good recovery was observed. These Nafion-free, vertically aligned Pt nanowires with surface roughness control show great promise as versatile electrochemical sensors and biosensors.

  11. Effects of Nanowire Length and Surface Roughness on the Electrochemical Sensor Properties of Nafion-Free, Vertically Aligned Pt Nanowire Array Electrodes

    PubMed Central

    Li, Zhiyang; Leung, Calvin; Gao, Fan; Gu, Zhiyong

    2015-01-01

    In this paper, vertically aligned Pt nanowire arrays (PtNWA) with different lengths and surface roughnesses were fabricated and their electrochemical performance toward hydrogen peroxide (H2O2) detection was studied. The nanowire arrays were synthesized by electroplating Pt in nanopores of anodic aluminum oxide (AAO) template. Different parameters, such as current density and deposition time, were precisely controlled to synthesize nanowires with different surface roughnesses and various lengths from 3 μm to 12 μm. The PtNWA electrodes showed better performance than the conventional electrodes modified by Pt nanowires randomly dispersed on the electrode surface. The results indicate that both the length and surface roughness can affect the sensing performance of vertically aligned Pt nanowire array electrodes. Generally, longer nanowires with rougher surfaces showed better electrochemical sensing performance. The 12 μm rough surface PtNWA presented the largest sensitivity (654 μA·mM−1·cm−2) among all the nanowires studied, and showed a limit of detection of 2.4 μM. The 12 μm rough surface PtNWA electrode also showed good anti-interference property from chemicals that are typically present in the biological samples such as ascorbic, uric acid, citric acid, and glucose. The sensing performance in real samples (river water) was tested and good recovery was observed. These Nafion-free, vertically aligned Pt nanowires with surface roughness control show great promise as versatile electrochemical sensors and biosensors. PMID:26404303

  12. Relationship between surface chemistry and electrochemical behavior of LiNi1/2Mn1/2O2 positive electrode in a lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Dupré, Nicolas; Martin, Jean-Frédéric; Oliveri, Julie; Soudan, Patrick; Yamada, Atsuo; Kanno, Ryoji; Guyomard, Dominique

    2011-05-01

    The formation and the evolution of lithium-containing species on the surface of grains of a layered 4 V material such as LiNi1/2Mn1/2O2 along the electrochemical cycling have been followed using 7Li MAS NMR, electrochemical impedance spectroscopy (EIS) and XPS. Materials displaying different specific surface areas and stored in different atmospheres have been investigated in order to study the influence of the surface/volume ratio and the influence of the initial surface state, respectively. It is shown that the presence of an initial interphase of Li2CO3 influences the electrochemical behavior of the electrode, emphasizing the importance of the history of the electrode prior cycling. 7Li MAS NMR experiments performed upon cycling indicate the formation of interphase species in reduction and their partial removal in oxidation, indicating the dynamic character of the interphase upon cycling. Combined NMR, EIS and XPS experiments show the strong influence of the electrode/electrolyte interphase evolution on the electrochemical performance. Such results lead us to draw conclusions on the optimal storage conditions of layered 4 V materials for Li-ion batteries such as LiNi1/2Mn1/2O2.

  13. Fluorescence Detected Surface Exafs (FDSEXAFS) of Iodine on Platinum: An Attempt to the in-sito Structure Determination of an Electrochemical Interface.

    DTIC Science & Technology

    1984-01-01

    new spectroscopic techniques such as surface enhanced raman siectroscopy (SzRS) (7) electrochemically modulated infra red reflectance spectroscopy...solution interface. Experimental: Experiments were performed in the A-2 station ( wiggler line) of the Cornell High Energy Synchrotron Source (CHESS

  14. Derivation of the fundamental equation of sound generated by moving aerodynamic surfaces

    NASA Technical Reports Server (NTRS)

    Aggarwal, H. R.

    1983-01-01

    Ffowcs Williams and Hawkings (1969) based their derivation of the fundamental equation of the sound generated by arbitrarily moving aerodynamic surfaces on the study of mass and momentum balance of a control volume imbedding a mathematical surface(s) exactly corresponding to real surface(s). These investigators also sketched an alternative method, employing generalized functions, for its derivation. This latter method, which was later developed by Farassat (1975), is purely mathematical and formal. Goldstein (1976) used the free-space Green function to produce an implicit derivation of the Ffowcs Williams and Hawkings equation. In the study presented here, Lowson's (1965) concept of moving point singularities is generalized to moving surface singularities, and a new derivation is given of the fundamental equation. The derivation is based on topological considerations of the underlying space, the fluid medium, and the integral properties of the Dirac delta function.

  15. Facile grafting of bioactive cellulose derivatives onto PVC surfaces

    NASA Astrophysics Data System (ADS)

    Bigot, Sandra; Louarn, Guy; Kébir, Nasreddine; Burel, Fabrice

    2013-10-01

    Bioactive methyl cellulose and hydroxyethyl cellulose were successfully grafted onto PVC films using a two-step pathway. PVC surface was first modified with isothiocyanate in DMSO/water medium. Then, unmodified polysaccharides were directly grafted onto the thiocyanated surface in acetonitrile/DMSO mixture, in presence of DBTL as catalyst. The polysaccharide grafting onto the PVC surface was evidenced by contact angle measurements, AFM and XPS.

  16. Stainless steel surface biofunctionalization with PMMA-bioglass coatings: compositional, electrochemical corrosion studies and microbiological assay.

    PubMed

    Floroian, L; Samoila, C; Badea, M; Munteanu, D; Ristoscu, C; Sima, F; Negut, I; Chifiriuc, M C; Mihailescu, I N

    2015-06-01

    A solution is proposed to surpass the inconvenience caused by the corrosion of stainless steel implants in human body fluids by protection with thin films of bioactive glasses or with composite polymer-bioactive glass nanostructures. Our option was to apply thin film deposition by matrix-assisted pulsed laser evaporation (MAPLE) which, to the difference to other laser or plasma techniques insures the protection of a more delicate material (a polymer in our case) against degradation or irreversible damage. The coatings composition, modification and corrosion resistance were investigated by FTIR and electrochemical techniques, under conditions which simulate their biological interaction with the human body. Mechanical testing demonstrates the adhesion, durability and resistance to fracture of the coatings. The coatings biocompatibility was assessed by in vitro studies and by flow cytometry. Our results support the unrestricted usage of coated stainless steel as a cheap alternative for human implants manufacture. They will be more accessible for lower prices in comparison with the majority present day fabrication of implants using Ti or Ti alloys.

  17. New metal based drugs: Spectral, electrochemical, DNA-binding, surface morphology and anticancer activity properties

    NASA Astrophysics Data System (ADS)

    Çeşme, Mustafa; Gölcü, Aysegul; Demirtaş, Ibrahim

    2015-01-01

    The NSAID piroxicam (PRX) drug was used for complex formation reactions with Cu(II), Zn(II) and Pt(II) metal salts have been synthesized. Then, these complexes have been characterized by spectroscopic and analytical techniques. Thermal behavior of the complexes were also investigated. The electrochemical properties of all complexes have been investigated by cyclic voltammetry (CV) using glassy carbon electrode. The biological activity of the complexes has been evaluated by examining their ability to bind to fish sperm double strand DNA (FSFSdsDNA) with UV spectroscopy. UV studies of the interaction of the PRX and its complexes with FSdsDNA have shown that these compounds can bind to FSdsDNA. The binding constants of the compounds with FSdsDNA have also been calculated. The morphology of the FSdsDNA, PRX, metal ions and metal complexes has been investigated by scanning electron microscopy (SEM). To get the SEM images, the interaction of compounds with FSdsDNA has been studied by means of differential pulse voltammetry (DPV) at FSdsDNA modified pencil graphite electrode (PGE). The decrease in intensity of the guanine oxidation signals has been used as an indicator for the interaction mechanism. The effect of proliferation PRX and complexes were examined on the HeLA and C6 cells using real-time cell analyzer with four different concentrations.

  18. Ambient synthesis, characterization, and electrochemical activity of LiFePO₄ nanomaterials derived from iron phosphate intermediates

    SciTech Connect

    Patete, Jonathan M.; Wong, Stanislaus S.; Scofield, Megan E.; Volkov, Vyacheslav; Koenigsmann, Christopher; Zhang, Yiman; Marschilok, Amy C.; Wang, Xiaoya; Bai, Jianming; Han, Jinkyu; Wang, Lei; Wang, Feng; Zhu, Yimei; Graetz, Jason A.

    2015-05-30

    LiFePO₄ materials have become increasingly popular as a cathode material due to the many benefits they possess including thermal stability, durability, low cost, and long life span. Nevertheless, to broaden the general appeal of this material for practical electrochemical applications, it would be useful to develop a relatively mild, reasonably simple synthesis method of this cathode material. Herein, we describe a generalizable, 2-step methodology of sustainably synthesizing LiFePO₄ by incorporating a template-based, ambient, surfactantless, seedless, U-tube protocol in order to generate size and morphologically tailored, crystalline, phase-pure nanowires. The purity, composition, crystallinity, and intrinsic quality of these wires were systematically assessed using transmission electron microscopy TEM, HRTEM, SEM, XRD, SAED, EDAX and high-resolution synchrotron XRD. From these techniques, we were able to determine that there is an absence of defects present in our wires, supporting the viability of our synthetic approach. Electrochemical analysis was also employed to assess their electrochemical activity. Although our nanowires do not contain any noticeable impurities, we attribute their less than optimal electrochemical rigor to differences in the chemical bonding between our LiFePO₄ nanowires and their bulk-like counterparts. Specifically, we demonstrate for the first time experimentally that the Fe-O3 chemical bond plays an important role in determining the overall conductivity of the material, an assertion which is further supported by recent first principles calculations. Nonetheless, our ambient, solution-based synthesis technique is capable of generating highly crystalline and phase-pure energy-storage-relevant nanowires that can be tailored so as to fabricate different sized materials of reproducible, reliable morphology.

  19. Ambient synthesis, characterization, and electrochemical activity of LiFePO₄ nanomaterials derived from iron phosphate intermediates

    DOE PAGES

    Patete, Jonathan M.; Wong, Stanislaus S.; Scofield, Megan E.; ...

    2015-05-30

    LiFePO₄ materials have become increasingly popular as a cathode material due to the many benefits they possess including thermal stability, durability, low cost, and long life span. Nevertheless, to broaden the general appeal of this material for practical electrochemical applications, it would be useful to develop a relatively mild, reasonably simple synthesis method of this cathode material. Herein, we describe a generalizable, 2-step methodology of sustainably synthesizing LiFePO₄ by incorporating a template-based, ambient, surfactantless, seedless, U-tube protocol in order to generate size and morphologically tailored, crystalline, phase-pure nanowires. The purity, composition, crystallinity, and intrinsic quality of these wires were systematicallymore » assessed using transmission electron microscopy TEM, HRTEM, SEM, XRD, SAED, EDAX and high-resolution synchrotron XRD. From these techniques, we were able to determine that there is an absence of defects present in our wires, supporting the viability of our synthetic approach. Electrochemical analysis was also employed to assess their electrochemical activity. Although our nanowires do not contain any noticeable impurities, we attribute their less than optimal electrochemical rigor to differences in the chemical bonding between our LiFePO₄ nanowires and their bulk-like counterparts. Specifically, we demonstrate for the first time experimentally that the Fe-O3 chemical bond plays an important role in determining the overall conductivity of the material, an assertion which is further supported by recent first principles calculations. Nonetheless, our ambient, solution-based synthesis technique is capable of generating highly crystalline and phase-pure energy-storage-relevant nanowires that can be tailored so as to fabricate different sized materials of reproducible, reliable morphology.« less

  20. The theory of cyclic voltammetry of electrochemically heterogeneous surfaces: comparison of different models for surface geometry and applications to highly ordered pyrolytic graphite.

    PubMed

    Ward, Kristopher R; Lawrence, Nathan S; Hartshorne, R Seth; Compton, Richard G

    2012-05-28

    The cyclic voltammetry at electrodes composed of multiple electroactive materials, where zones of one highly active material are distributed over a substrate of a second, less active material, is investigated by simulation. The two materials are assumed to differ in terms of their electrochemical rate constants towards any given redox couple. For a one-electron oxidation or reduction, the effect on voltammetry of the size and relative surface coverages of the zones as well as the rate constant of the slower zone are considered for systems where it is much slower than the rate constant of the faster zones. The occurrence of split peak cyclic voltammetry where two peaks are observed in the forward sweep, is studied in terms of the diffusional effects present in the system. A number of surface geometries are compared: specifically the more active zones are modelled as long, thin bands, as steps in the surface, as discs, and as rings (similar to a partially blocked electrode). Similar voltammetry for the band, step and ring models is seen but the disc geometry shows significant differences. Finally, the simulation technique is applied to the modelling of highly-ordered pyrolytic graphite (HOPG) surface and experimental conditions under which it may be possible to observe split peak voltammetry are predicted.

  1. Electrochemical oxidation of guanine: electrode reaction mechanism and tailoring carbon electrode surfaces to switch between adsorptive and diffusional responses.

    PubMed

    Li, Qian; Batchelor-McAuley, Christopher; Compton, Richard G

    2010-06-03

    The electrochemical oxidation of guanine is studied in aqueous media at various carbon electrodes. Specifically edge plane pyrolytic graphite (EPPG), basal plane pyrolytic graphite (BPPG), and highly ordered pyrolytic graphite (HOPG) were used, and the voltammetry was found to vary significantly. In all cases, signals characteristic of adsorbed guanine were seen and the total charge passed varied from surface to surface in the order roughened BPPG > EPPG > BPPG > HOPG. It is of note that the peak height for the EPPG electrode is less than that found for roughened BPPG; furthermore, across the series of electrodes, there is a significant decrease in peak potential with increasing density of edge plane sites present at the electrode surface. This leads us to conclude that there are two dominating and controlling factors present: (i) the density of basal plane sites on which guanine can adsorb and (ii) the density of edge plane sites necessary for the electro-oxidation of the analyte. This conclusion is corroborated through further experiments with multi- and single-walled carbon nanotubes. Adsorption was seen to be enhanced by modification of the EPPG surface with alumina particles, and as such, increased peak signals were observed in their presence. It is further reported that via the pre-adsorption of acetone onto the graphite surface that the adsorption of guanine may be blocked, resulting in a diffusional voltammetric signal. This diffusional response has been successfully modeled and gives insight into the complex -4e(-), -4H(+) oxidation mechanism; specifically, it enables explanation of the observed change in rate-determining step with scan rate. The oxidation of guanine first proceeds via a two-electron oxidation followed by a chemical step to form 8-oxoguanine, then 8-oxoguanine is then further oxidized to form nonelectroactive products. The change is mechanism is attributed to the variation in potential of the first and second electron transfer with scan

  2. Why Do We Need the Derivative for the Surface Area?

    ERIC Educational Resources Information Center

    Hristova, Yulia; Zeytuncu, Yunus E.

    2016-01-01

    Surface area and volume computations are the most common applications of integration in calculus books. When computing the surface area of a solid of revolution, students are usually told to use the frustum method instead of the disc method; however, a rigorous explanation is rarely provided. In this note, we provide one by using geometric…

  3. Characterization of surface active materials derived from farm products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Surface active materials obtained by chemical modification of plant protein isolates (lupin, barley, oat), corn starches (dextrin, normal, high amylose, and waxy) and soybean oil (soybean oil based polysoaps, SOPS) were investigated for their surface and interfacial properties using axisymmetric dro...

  4. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface.

    PubMed

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; Crumlin, Ethan J; Yildiz, Bilge

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.

  5. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

    NASA Astrophysics Data System (ADS)

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; Crumlin, Ethan J.; Yildiz, Bilge

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a `volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.

  6. Novel fluorescent 1,8-naphthalimide derivatives containing thiophene and pyrazole moieties: Synthesis by direct C-H arylation and evaluation of photophysical and electrochemical properties

    NASA Astrophysics Data System (ADS)

    Jin, Zhengneng; Wu, Jiashou; Wang, Chuanfeng; Dai, Guoliang; Liu, Shiyong; Lu, Jianmei; Jiang, Huajiang

    2014-01-01

    A series of novel 1,8-naphthalimide derivatives containing thiophene and pyrazole moities were synthesized by direct Pd-catalyzed C-H arylation and then characterized by 1H NMR, 13C NMR, MALDI-HRMS, and elementary analysis. The photophysical and electrochemical properties of the derivatives were also investigated. All compounds have green emission both in diluted CH2Cl2 solution and solid film. The cyclic voltammetry (CV) measurements showed that the target compounds had a lowest unoccupied molecular orbital (LUMO) range from -3.49 eV to -3.29 eV and a highest occupied molecular orbital (HOMO) range from -6.04 eV to -5.81 eV. Quantum chemical calculations were performed to obtain the optimized ground-state geometry as well as the spatial distributions of the HOMO, LUMO levels of the compounds.

  7. Novel fluorescent 1,8-naphthalimide derivatives containing thiophene and pyrazole moieties: synthesis by direct C-H arylation and evaluation of photophysical and electrochemical properties.

    PubMed

    Jin, Zhengneng; Wu, Jiashou; Wang, Chuanfeng; Dai, Guoliang; Liu, Shiyong; Lu, Jianmei; Jiang, Huajiang

    2014-01-03

    A series of novel 1,8-naphthalimide derivatives containing thiophene and pyrazole moities were synthesized by direct Pd-catalyzed C-H arylation and then characterized by (1)H NMR, (13)C NMR, MALDI-HRMS, and elementary analysis. The photophysical and electrochemical properties of the derivatives were also investigated. All compounds have green emission both in diluted CH2Cl2 solution and solid film. The cyclic voltammetry (CV) measurements showed that the target compounds had a lowest unoccupied molecular orbital (LUMO) range from -3.49 eV to -3.29 eV and a highest occupied molecular orbital (HOMO) range from -6.04 eV to -5.81 eV. Quantum chemical calculations were performed to obtain the optimized ground-state geometry as well as the spatial distributions of the HOMO, LUMO levels of the compounds.

  8. Simultaneous deposition of diamondlike carbon films on both surfaces of aluminum substrate by electrochemical technique

    NASA Astrophysics Data System (ADS)

    Li, R. S.; Zhou, M.; Pan, X. J.; Zhang, Z. X.; Lu, B. A.; Wang, T.; Xie, E. Q.

    2009-03-01

    By electrolysis of the N ,N-dimethylformamide solution, an attempt was made to simultaneously deposit diamondlike carbon (DLC) films on both surfaces of an aluminum (Al) substrate. Raman spectra showed that the structures of the DLC film were uniform. The thickness distribution of the film was 260-300 nm. A simple model of the sustaining mechanism was proposed for simultaneous electrodeposition of the DLC film on both surfaces of conductive substrates. The simultaneous formation of the DLC film on both surfaces of the Al substrate showed a possibility in the three-dimensional deposition of DLC films on complex conductive substrates.

  9. Monitoring Surface Climate With its Emissivity Derived From Satellite Measurements

    NASA Technical Reports Server (NTRS)

    Zhou, Daniel K.; Larar, Allen M.; Liu, Xu

    2012-01-01

    Satellite thermal infrared (IR) spectral emissivity data have been shown to be significant for atmospheric research and monitoring the Earth fs environment. Long-term and large-scale observations needed for global monitoring and research can be supplied by satellite-based remote sensing. Presented here is the global surface IR emissivity data retrieved from the last 5 years of Infrared Atmospheric Sounding Interferometer (IASI) measurements observed from the MetOp-A satellite. Monthly mean surface properties (i.e., skin temperature T(sub s) and emissivity spectra epsilon(sub v) with a spatial resolution of 0.5x0.5-degrees latitude-longitude are produced to monitor seasonal and inter-annual variations. We demonstrate that surface epsilon(sub v) and T(sub s) retrieved with IASI measurements can be used to assist in monitoring surface weather and surface climate change. Surface epsilon(sub v) together with T(sub s) from current and future operational satellites can be utilized as a means of long-term and large-scale monitoring of Earth 's surface weather environment and associated changes.

  10. Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

    SciTech Connect

    Meng, Jianbing Dong, Xiaojuan; Wei, Xiuting; Yin, Zhanmin

    2014-03-15

    Hard anti-adhesion surfaces, with low roughness and wear resistance, on aluminium substrates of rubber plastic moulds were fabricated via a new coupling method of liquid plasma and electrochemical machining. With the aid of liquid plasma thermal polishing and electrochemical anodic dissolution, micro/nano-scale binary structures were prepared as the base of the anti-adhesion surfaces. The anti-adhesion behaviours of the resulting aluminium surfaces were analysed by a surface roughness measuring instrument, a scanning electron microscope (SEM), a Fourier-transform infrared spectrophotometer (FTIR), an X-ray diffractometer (XRD), an optical contact angle meter, a digital Vickers micro-hardness (Hv) tester, and electronic universal testing. The results show that, after the liquid plasma and electrochemical machining, micro/nano-scale binary structures composed of micro-scale pits and nano-scale elongated boss structures were present on the sample surfaces. As a result, the anti-adhesion surfaces fabricated by the above coupling method have good anti-adhesion properties, better wear resistance and lower roughness.

  11. Structure Effects on the Energetics of the Electrochemical Reduction of CO2 by Copper Surfaces

    SciTech Connect

    Durand, William

    2011-08-19

    Polycrystalline copper electrocatalysts have been experimentally shown to be capable of reducing CO{sub 2} into CH{sub 4} and C{sub 2}H{sub 4} with relatively high selectivity, and a mechanism has recently been proposed for this reduction on the fcc(211) surface of copper, which was assumed to be the most active facet. In the current work, we use computational methods to explore the effects of the nanostructure of the copper surface and compare the effects of the fcc(111), fcc(100) and fcc(211) facets of copper on the energetics of the electroreduction of CO{sub 2}. The calculations performed in this study generally show that the intermediates in CO{sub 2} reduction are most stabilized by the (211) facet, followed by the (100) facet, with the (111) surface binding the adsorbates most weakly. This leads to the prediction that the (211) facet is the most active surface among the three in producing CH{sub 4} from CO{sub 2}, as well as the by-products H{sub 2} and CO. HCOOH production may be mildly enhanced on the more close-packed surfaces ((111) and (100)) as compared to the (211) facet, due to a change in mechanism from a carboxyl intermediate to a formate intermediate. The results are compared to experimental data on these same surfaces; the predicted trends in voltage requirements are consistent between the experimental and computational data.

  12. Electrochemical biosensors for detection of point mutation based on surface ligation reaction and oligonucleotides modified gold nanoparticles.

    PubMed

    Wang, Qing; Yang, Lijuan; Yang, Xiaohai; Wang, Kemin; He, Leiliang; Zhu, Jinqing

    2011-03-04

    An electrochemical method for point mutation detection based on surface ligation reaction and oligonucleotides (ODNs) modified gold nanoparticles (AuNPs) was demonstrated. Point mutation identification was achieved using Escherichia coli DNA ligase. This system for point mutation detection relied on a sandwich assay comprising capture ODN immobilized on Au electrodes, target ODN and ligation ODN. Because of the sequence-specific surface reactions of E. coli DNA ligase, the ligation ODN covalently linked to the capture ODN only in the presence of a perfectly complementary target ODN. The presence of ligation products on Au electrode was detected using chronocoulometry through hybridization with reporter ODN modified AuNPs. The use of AuNPs improved the sensitivity of chronocoulometry in this approach, a detection limit of 0.9 pM complementary ODN was obtained. For single base mismatched ODN (smODN), a negligible signal was observed. Even if the concentration ratio of complementary ODN to smODN was decreased to 1:1000, a detectable signal was observed. This work may provide a specific, sensitive and cost-efficient approach for point mutant detection.

  13. Experimental Approach to Controllably Vary Protein Oxidation While Minimizing Electrode Adsorption for Boron-Doped Diamond Electrochemical Surface Mapping Applications

    SciTech Connect

    McClintock, Carlee; Hettich, Robert {Bob} L

    2013-01-01

    Oxidative protein surface mapping has become a powerful approach for measuring the solvent accessibility of folded protein structures. A variety of techniques exist for generating the key reagent hydroxyl radicals for these measurements; however, many of these approaches require use of radioactive sources or caustic oxidizing chemicals. The purpose of this research was to evaluate and optimize the use of boron-doped diamond (BDD) electrochemistry as a highly accessible tool for producing hydroxyl radicals as a means to induce a controllable level of oxidation on a range of intact proteins. These experiments utilize a relatively high flow rates to reduce protein residence time inside the electrochemical flow chamber, along with a unique cell activation approach to improve control over the intact protein oxidation yield. Studies were conducted to evaluate the level of protein adsorption onto the electrode surface. This report demonstrates a robust protocol for the use of BDD electrochemistry and high performance LC-MS/MS as a high-throughput experimental pipeline for probing higher order protein structure, and illustrates how it is complementary to predictive computational modeling efforts.

  14. Derived Land Surface Emissivity From Suomi NPP CrIS

    NASA Technical Reports Server (NTRS)

    Zhou, Daniel K.; Larar, Allen M.; Liu, Xu

    2012-01-01

    Presented here is the land surface IR spectral emissivity retrieved from the Cross-track Infrared Sounder (CrIS) measurements. The CrIS is aboard the Suomi National Polar-orbiting Partnership (NPP) satellite launched on October 28, 2011. We describe the retrieval algorithm, demonstrate the surface emissivity retrieved with CrIS measurements, and inter-comparison with the Infrared Atmospheric Sounding Interferometer (IASI) emissivity. We also demonstrate that surface emissivity from satellite measurements can be used in assistance of monitoring global surface climate change, as a long-term measurement of IASI and CrIS will be provided by the series of EUMETSAT MetOp and US Joint Polar Satellite System (JPSS) satellites. Monthly mean surface properties are produced using last 5-year IASI measurements. A temporal variation indicates seasonal diversity and El Nino/La Nina effects not only shown on the water but also on the land. Surface spectral emissivity and skin temperature from current and future operational satellites can be utilized as a means of long-term monitoring of the Earth's environment. CrIS spectral emissivity are retrieved and compared with IASI. The difference is small and could be within expected retrieval error; however it is under investigation.

  15. Spectral surface albedo derived from GOME-2/Metop measurements

    NASA Astrophysics Data System (ADS)

    Pflug, Bringfried; Loyola, Diego

    2009-09-01

    Spectral surface albedo is an important input for GOME-2 trace gas retrievals. An algorithm was developed for estimation of spectral surface albedo from top-of-atmosphere (TOA)-radiances measured by the Global Ozone Monitoring Experiment GOME-2 flying on-board MetOp-A. The climatologically version of this algorithm estimates Minimum Lambert-Equivalent Reflectivity (MLER) for a fixed time window and can use data of many years in contrast to the Near-real time version. Accuracy of surface albedo estimated by MLER-computation increases with the amount of available data. Unfortunately, most of the large GOME pixels are partly covered by clouds, which enhance the LER-data. A plot of LER-values over cloud fraction is used within this presentation to account for this influence of clouds. This "cloud fraction plot" can be applied over all surface types. Surface albedo obtained using the "cloud fraction plot" is compared with reference surface albedo spectra and with the FRESCO climatology. There is a general good agreement; however there are also large differences for some pixels.

  16. Sweep flocculation and adsorption of viruses on aluminum flocs during electrochemical treatment prior to surface water microfiltration.

    PubMed

    Tanneru, Charan Tej; Rimer, Jeffrey D; Chellam, Shankararaman

    2013-05-07

    Bench-scale experiments were performed to evaluate virus control by an integrated electrochemical-microfiltration (MF) process from turbid (15 NTU) surface water containing moderate amounts of dissolved organic carbon (DOC, 5 mg C/L) and calcium hardness (50 mg/L as CaCO3). Higher reductions in MS2 bacteriophage concentrations were obtained by aluminum electrocoagulation and electroflotation compared with conventional aluminum sulfate coagulation. This was attributed to electrophoretic migration of viruses, which increased their concentrations in the microenvironment of the sacrificial anode where coagulant precursors are dissolved leading to better destabilization during electrolysis. In all cases, viruses were not inactivated implying measured reductions were solely due to their removal. Sweep flocculation was the primary virus destabilization mechanism. Direct evidence for virus enmeshment in flocs was provided by two independent methods: quantitative elution using beef extract at elevated pH and quantitating fluorescence from labeled viruses. Atomic force microscopy studies revealed a monotonically increasing adhesion force between viruses immobilized on AFM tips and floc surfaces with electrocoagulant dosage, which suggests secondary contributions to virus uptake on flocs from adsorption. Virus sorption mechanisms include charge neutralization and hydrophobic interactions with natural organic matter removed during coagulation. This also provided the basis for interpreting additional removal of viruses by the thick cake formed on the surface of the microfilter following electrocoagulation. Enhancements in virus removal as progressively more aluminum was electrolyzed therefore embodies contributions from (i) better encapsulation onto greater amounts of fresh Al(OH)3 precipitates, (ii) increased adsorption capacity associated with higher available coagulant surface area, (iii) greater virus-floc binding affinity due to effective charge neutralization and

  17. Rational Design of Bi Nanoparticles for Efficient Electrochemical CO2 Reduction: The Elucidation of Size and Surface Condition Effects

    SciTech Connect

    Zhang, Zhiyong; Chi, Miaofang; Veith, Gabriel M.; Zhang, Pengfei; Lutterman, Daniel A.; Rosenthal, Joel; Overbury, Steven H.; Dai, Sheng; Zhu, Huiyuan

    2016-08-08

    Here we report an efficient electrochemical conversion of CO2 to CO on surface-activated bismuth nanoparticles (NPs) in acetonitrile (MeCN) under ambient conditions, with the assistance of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]). Through the comparison between electrodeposited Bi films (Bi-ED) and different types of Bi NPs, we, for the first time, demonstrate the effects of catalyst’s size and surface condition on organic phase electrochemical CO2 reduction. Our study reveals that the surface inhibiting layer (hydrophobic surfactants and Bi3+ species) formed during the synthesis and purification process hinders the CO2 reduction, leading to a 20% drop in Faradaic efficiency for CO evolution (FECO). Bi particle size showed a significant effect on FECO when the surface of Bi was air-oxidized, but this effect of size on FECO became negligible on surface-activated Bi NPs. After the surface activation (hydrazine treatment) that effectively removed the native inhibiting layer, activated 36-nm Bi NPs exhibited an almost-quantitative conversion of CO2 to CO (96.1% FECO), and a mass activity for CO evolution (MACO) of 15.6 mA mg–1, which is three-fold higher than the conventional Bi-ED, at ₋2.0 V (vs Ag/AgCl). Ultimately, this work elucidates the importance of the surface activation for an efficient electrochemical CO2 conversion on metal NPs and paves the way for understanding the CO2 electrochemical reduction mechanism in nonaqueous media.

  18. Surface-enhanced Raman difference between bombesin and its modified analogues on the colloidal and electrochemically roughen silver surfaces.

    PubMed

    Podstawka, Edyta; Ozaki, Yukihiro

    2008-10-01

    In this article, surface-enhanced Raman scattering (SERS) spectra of bombesin (BN) and its six modified analogues ([D-Phe(12)]BN, [Tyr(4)]BN, [Tyr(4),D-Phe(12)]BN, [D-Phe(12),Leu(14)]BN, [Leu(13)-(R)-Leu(14)]BN, and [Lys(3)]BN) on a colloidal silver surface are reported and compared with SERS spectra of these species immobilized onto an ellectrochemically roughen silver electrode. Changes in enhancement and wavenumber of proper bands upon adsorption on different silver surfaces are consistent with BN and its analogues adsorption primarily through Trp(8). Slightly different adsorption states of these molecules are observed depending upon natural amino acids substitution. For example, the indole ring in all the peptides interacts with silver nanoparticles in a edge-on orientation. It is additionally coordinated to the silver through the N(1)--H bond for all the peptides, except [Phe(12)]BN. This is in contrary to the results obtained for the silver roughen electrode that show direct but not strong N(1)--H/Ag interaction for all peptides except [D-Phe(12),Leu(14)]BN and [Leu(13)-(R)-Leu(14)]BN. For BN only C==O is not involved in the chemical coordination with the colloidal surface. [Lys(3)]BN and BN also adsorb with the C--N bond of NH(2) group normal and horizontal, respectively, to the colloidal surface, whereas C--NH(2) in other peptides is tilted to this surface. Also, the Trp(8) --CH(2)-- moiety of only [Tyr(4)]BN, [Lys(3)]BN, and [Tyr(4),D-Phe(12)]BN coordinates to Ag, whereas the Phe(12) ring of [Phe(12)]BN, [Tyr(4),D-Phe(12)]BN, and [D-Phe(12),Leu(14)]BN assists in the peptides binding only on the colloidal silver.

  19. Interactions between glycine derivatives and mineral surfaces: Implications for the origins of life on planetary surfaces

    NASA Astrophysics Data System (ADS)

    Marshall-Bowman, K. J.; Cleaves, H. J.; Sverjensky, D. A.; Hazen, R. M.

    2009-12-01

    Various mechanisms could have delivered amino acids to the prebiotic Earth (Miller and Orgel 1974). The polymerization of amino acids may have been important for the origin of life, as peptides may have been components for the first self-replicating systems (Kauffman 1971; Yao et al 1998). Though amino acid concentrations in the primitive oceans were likely too dilute for significant oligomerization to occur (Cleaves et al 2009), mineral surface adsorption may have concentrated these biomolecules (Bernal 1951; Lambert 2008). Few studies have examined the catalytic effects of mineral surfaces on aqueous peptide oligomerization or degradation. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied the reverse reaction of polymer degradation to measure potential mineral catalysis. Glycine (G) derivatives glycylglycine (GG), diketopiperazine (DKP), and glycylglycylglycine (GGG) were reacted with different minerals (calcite, hematite, montmorillonite, rutile, amorphous silica, and pyrite) in the presence of 0.05 M pH 8.1 KHCO3 buffer and 0.1 M NaCl as background electrolyte. Experiments were performed by reacting the aqueous amino acid derivative-mineral mixtures in a thermostatted oven (modified to accommodate a mechanical rotator) at 25°, 50° or 70°C. Samples were removed after 30, 60, 90, and 140 hours. Samples were then analyzed using high performance liquid chromatography to quantify the products. Besides mineral catalysis, it was determined that degradation of GGG proceeds principally via a GGG → DKP + G mechanism, rather than via GGG → GG + G. Below 70°C kinetics were generally too sluggish to detect catalytic activity over reasonable laboratory time-scales at this pH. At 70°C, pyrite was the only mineral with detectible catalytic effects on the degradation of GGG. GGG degraded ~ 1.5 - 4 x faster in the presence of pyrite than in control reactions, depending on the ratio of solution

  20. A new fluorescent and electrochemical Zn2+ ion sensor based on Schiff base derived from benzil and L-tryptophan.

    PubMed

    Dutta, Kaku; Deka, Ramesh C; Das, Diganta Kumar

    2014-04-24

    Single molecule acting as both fluorescent and electrochemical sensor for Zn(2+) ion is rare. The product (L) obtained on condensation between benzil and L-tryptophan has been characterized by H NMR, ESI-MS and FT-IR spectroscopy. L in 1:1 (v/v) CH3OH:H2O solution shows fluorescence emission in the range 300 nm to 600 nm with λmax at 350 nm when is excited with 295 nm photon. Zn(2+) ion could induce a 10-fold enhancement in fluorescent intensity of L. Fluorescence and UV/Visible spectral data analysis shows that the binding ratio between Zn(2+) ion and L is 1:1 with log β=4.55. Binding of Zn(2+) ion disrupts the photoinduced electron transfer (PET) process in L and causes the fluorescence intensity enhancement. When cyclic voltammogram is recorded for L in 1:1 (v/v) CH3OH:H2O using glassy carbon (GC) electrode, two quasi reversible redox couples at redox potential values -0.630±0.005 V and -1.007±0.005 V are obtained (Ag-AgCl as reference, scan rate 0.1 V s(-1)). Interaction with Zn(2+) ion makes the first redox couple irreversible while the second couple undergoes a 0.089 V positive shift in redox potential. Metal ions - Cd(2+), Cu(2+), Co(2+), Hg(2+), Ag(+), Ni(2+), Fe(2+), Mn(2+), Mg(2+), Ca(2+)and Pb(2+), individually or all together, has no effect on the fluorescent as well as electrochemical property of L. DFT calculations showed that Zn(2+) ion binds to L to form a stable complex. The detection limit for both fluorescence as well as electrochemical detection was 10(-6) M.

  1. Functionalized Solid Electrodes for Electrochemical Biosensing of Purine Nucleobases and Their Analogues: A Review

    PubMed Central

    Sharma, Vimal Kumar; Jelen, Frantisek; Trnkova, Libuse

    2015-01-01

    Interest in electrochemical analysis of purine nucleobases and few other important purine derivatives has been growing rapidly. Over the period of the past decade, the design of electrochemical biosensors has been focused on achieving high sensitivity and efficiency. The range of existing electrochemical methods with carbon electrode displays the highest rate in the development of biosensors. Moreover, modification of electrode surfaces based on nanomaterials is frequently used due to their extraordinary conductivity and surface to volume ratio. Different strategies for modifying electrode surfaces facilitate electron transport between the electrode surface and biomolecules, including DNA, oligonucleotides and their components. This review aims to summarize recent developments in the electrochemical analysis of purine derivatives, as well as discuss different applications. PMID:25594595

  2. Developing satellite-derived estimates of surface moisture status

    NASA Technical Reports Server (NTRS)

    Nemani, Ramakhrishna; Pierce, Lars; Running, Steve; Goward, Samuel

    1993-01-01

    An evaluation is made of the remotely sensed surface temperature (Ts)/normalized difference vegetation index (NDVI) relationship in studies of the influence of biome type on the slope of Ts/NDVI, and of the automation of the process of defining the relationship so that the surface moisture status can be compared with Ts/NDVI at continental scales. The analysis is conducted using the NOAA AVHRR over a 300 x 300 km area in western Montana, as well as biweekly composite AVHRR data. A strong negative relationship is established between NDVI and Ts over all biome types.

  3. The electrochemical properties of the purine bases : at the interface between biological conjugates to inorganic surfaces

    NASA Technical Reports Server (NTRS)

    Hays, Charles C.

    2003-01-01

    The study of the charge transfer and interfacial reactions of the purine bases in physiological solutions provides valuable knowledge, as these processes are relevant to the origins of life. It has been proposed that the adsorption of the adsorption of the purine bases on an inorganic surface could serve as a template for specifying the arrangement of amino acids in peptides.

  4. Reproducibility of crop surface maps extracted from Unmanned Aerial Vehicle (UAV) derived digital surface maps

    NASA Astrophysics Data System (ADS)

    Parkes, Stephen D.; McCabe, Matthew F.; Al-Mashhawari, Samir K.; Rosas, Jorge

    2016-10-01

    Crop height measured from UAVs fitted with commercially available RGB cameras provide an affordable alternative to retrieve field scale high resolution estimates. The study presents an assessment of between flight reproducibility of Crop Surface Maps (CSM) extracted from Digital Surface Maps (DSM) generated by Structure from Motion (SfM) algorithms. Flights were conducted over a centre pivot irrigation system covered with an alfalfa crop. An important step in calculating the absolute crop height from the UAV derived DSM is determining the height of the underlying terrain. Here we use automatic thresholding techniques applied to RGB vegetation index maps to classify vegetated and soil pixels. From interpolation of classified soil pixels, a terrain map is calculated and subtracted from the DSM. The influence of three different thresholding techniques on CSMs are investigated. Median Alfalfa crop heights determined with the different thresholding methods varied from 18cm for K means thresholding to 13cm for Otsu thresholding methods. Otsu thresholding also gave the smallest range of crop heights and K means thresholding the largest. Reproducibility of median crop heights between flight surveys was 4-6cm for all thresholding techniques. For the flight conducted later in the afternoon shadowing caused soil pixels to be classified as vegetation in key locations around the domain, leading to lower crop height estimates. The range of crop heights was similar for both flights using K means thresholding (35-36cm), local minimum thresholding depended on whether raw or normalised RGB intensities were used to calculate vegetation indices (30-35cm), while Otsu thresholding had a smaller range of heights and varied most between flights (26-30cm). This study showed that crop heights from multiple survey flights are comparable, however, they were dependent on the thresholding method applied to classify soil pixels and the time of day the flight was conducted.

  5. Structural and electrochemical properties of nanostructured nickel silicides by reduction and silicification of high-surface-area nickel oxide

    SciTech Connect

    Chen, Xiao; Zhang, Bingsen; Li, Chuang; Shao, Zhengfeng; Su, Dangsheng; Williams, Christopher T.; Liang, Changhai

    2012-03-15

    Graphical abstract: Nanostructured nickel silicides have been synthesized by reduction and silification of high-surface-area nickel oxide, and exhibited remarkably like-noble metal property, lower electric resistivity, and ferromagnetism at room temperature. Highlights: Black-Right-Pointing-Pointer NiSi{sub x} have been prepared by reduction and silification of high-surface-area NiO. Black-Right-Pointing-Pointer The structure of nickel silicides changed with increasing reaction temperature. Black-Right-Pointing-Pointer Si doping into nickel changed the magnetic properties of metallic nickel. Black-Right-Pointing-Pointer NiSi{sub x} have remarkably lower electric resistivity and like-noble metal property. -- Abstract: Nanostructured nickel silicides have been prepared by reduction and silicification of high-surface-area nickel oxide (145 m{sup 2} g{sup -1}) produced via precipitation. The prepared materials were characterized by nitrogen adsorption, X-ray diffraction, thermal analysis, FT-IR spectroscopy, scanning electron microscopy, transmission electron microscopy, magnetic and electrochemical measurements. The nickel silicide formation involves the following sequence: NiO (cubic) {yields} Ni (cubic) {yields} Ni{sub 2}Si (orthorhombic) {yields} NiSi (orthorhombic) {yields} NiSi{sub 2} (cubic), with particles growing from 13.7 to 21.3 nm. The nickel silicides are ferromagnetic at room temperature, and their saturation magnetization values change drastically with the increase of Si content. Nickel silicides have remarkably low electrical resistivity and noble metal-like properties because of a constriction of the Ni d band and an increase of the electronic density of states. The results suggest that such silicides are promising candidates as inexpensive yet functional materials for applications in electrochemistry as well as catalysis.

  6. Electrochemical immobilization of Fluorescent labelled probe molecules on a FTO surface for affinity detection based on photo-excited current

    NASA Astrophysics Data System (ADS)

    Haruyama, Tetsuya; Wakabayashi, Ryo; Cho, Takeshi; Matsuyama, Sho-taro

    2011-10-01

    Photo-excited current can be generated at a molecular interface between a photo-excited molecules and a semi-conductive material in appropriate condition. The system has been recognized for promoting photo-energy devices such as an organic dye sensitized solar-cell. The photo-current generated reactions are totally dependent on the interfacial energy reactions, which are in a highly fluctuated interfacial environment. The authors investigated the photo-excited current reaction to develop a smart affinity detection method. However, in order to perform both an affinity reaction and a photo-excited current reaction at a molecular interface, ordered fabrications of the functional (affinity, photo-excitation, etc.) molecules layer on a semi-conductive surface is required. In the present research, we would like to present the fabrication and functional performance of photo-excited current-based affinity assay device and its application for detection of endocrine disrupting chemicals. On the FTO surface, fluorescent pigment labelled affinity peptide was immobilized through the EC tag (electrochemical-tag) method. The modified FTO produced a current when it was irradiated with diode laser light. However, the photo current decreased drastically when estrogen (ES) coexisted in the reaction solution. In this case, immobilized affinity probe molecules formed a complex with ES and estrogen receptor (ER). The result strongly suggests that the photo-excited current transduction between probe molecule-labelled cyanine pigment and the FTO surface was partly inhibited by a complex that formed at the affinity oligo-peptide region in a probe molecule on the FTO electrode. The bound bulky complex may act as an impediment to perform smooth transduction of photo-excited current in the molecular interface. The present system is new type of photo-reaction-based analysis. This system can be used to perform simple high-sensitive homogeneous assays.

  7. Novel polymer Li-ion binder carboxymethyl cellulose derivative enhanced electrochemical performance for Li-ion batteries.

    PubMed

    Qiu, Lei; Shao, Ziqiang; Wang, Daxiong; Wang, Feijun; Wang, Wenjun; Wang, Jianquan

    2014-11-04

    Novel water-based binder lithium carboxymethyl cellulose (CMC-Li) is synthesized by cotton as raw material. The mechanism of the CMC-Li as a binder is reported. Electrochemical properties of batteries' cathodes based on commercially available lithium iron phosphate (LiFePO4, LFP) and water-soluble binder are investigated. Sodium carboxymethyl cellulose (CMC-Na, CMC) and CMC-Li are used as the binder. After 200 cycles, compared with conventional poly(vinylidene fluoride) (PVDF) binder, the CMC-Li binder significantly improves cycling performance of the LFP cathode 96.7% of initial reversible capacity achieved at 175 mA h g(-1). Constant current charge-discharge test results demonstrate that the LFP electrode using CMC-Li as the binder has the highest rate capability, followed closely by those using CMC and PVDF binders, respectively. Electrochemical impedance spectroscopy test results show that the electrode using CMC-Li as the binder has lower charge transfer resistance than the electrodes using CMC and PVDF as the binders.

  8. Potential amoebicidal activity of hydrazone derivatives: synthesis, characterization, electrochemical behavior, theoretical study and evaluation of the biological activity.

    PubMed

    Toledano-Magaña, Yanis; García-Ramos, Juan Carlos; Navarro-Olivarria, Marisol; Flores-Alamo, Marcos; Manzanera-Estrada, Mayra; Ortiz-Frade, Luis; Galindo-Murillo, Rodrigo; Ruiz-Azuara, Lena; Meléndrez-Luevano, Ruth Ma; Cabrera-Vivas, Blanca M

    2015-05-29

    Four new hydrazones were synthesized by the condensation of the selected hydrazine and the appropriate nitrobenzaldehyde. A complete characterization was done employing 1H- and 13C-NMR, electrochemical techniques and theoretical studies. After the characterization and electrochemical analysis of each compound, amoebicidal activity was tested in vitro against the HM1:IMSS strain of Entamoeba histolytica. The results showed the influence of the nitrobenzene group and the hydrazone linkage on the amoebicidal activity. meta-Nitro substituted compound 2 presents a promising amoebicidal activity with an IC50 = 0.84 μM, which represents a 7-fold increase in cell growth inhibition potency with respect to metronidazole (IC50 = 6.3 μM). Compounds 1, 3, and 4 show decreased amoebicidal activity, with IC50 values of 7, 75 and 23 µM, respectively, as a function of the nitro group position on the aromatic ring. The observed differences in the biological activity could be explained not only by the redox potential of the molecules, but also by their capacity to participate in the formation of intra- and intermolecular hydrogen bonds. Redox potentials as well as the amoebicidal activity can be described with parameters obtained from the DFT analysis.

  9. Synthesis and Electrochemical Characterization of M2Mn3O8 (M=Ca,Cu) Compounds and Derivatives

    SciTech Connect

    Park, Yong Joon; Doeff, Marca M.

    2005-08-25

    M{sub 2}Mn{sub 3}O{sub 8} (M=Ca{sup 2+}, Cu{sup 2+}) compounds were synthesized and characterized in lithium cells. The M{sup 2+} cations, which reside in the van der Waal's gaps between adjacent sheets of Mn{sub 3}O{sub 8}{sup 4-}, may be replaced chemically (by ion-exchange) or electrochemically with Li. More than 7 Li{sup +}/Cu{sub 2}Mn{sub 3}O{sub 8} may be inserted electrochemically, with concomitant reduction of Cu{sup 2+} to Cu metal, but less Li can be inserted into Ca{sub 2}Mn{sub 3}O{sub 8}. In the case of Cu{sup 2+}, this process is partially reversible when the cell is charged above 3.5 V vs. Li, but intercalation of Cu{sup +} rather than Cu{sup 2+} and Li{sup +}/Cu{sup +} exchange occurs during the subsequent discharge. If the cell potential is kept below 3.4 V, the Li in excess of 4Li{sup +}/Cu{sub 2}Mn{sub 3}O{sub 8} can be cycled reversibly. The unusual mobility of +2 cations in a layered structure has important implications both for the design of cathodes for Li batteries and for new systems that could be based on M{sup 2+} intercalation compounds.

  10. Electrochemical Sensors Based on Screen-Printed Electrodes: The Use of Phthalocyanine Derivatives for Application in VFA Detection

    PubMed Central

    Ndiaye, Amadou L.; Delile, Sébastien; Brunet, Jérôme; Varenne, Christelle; Pauly, Alain

    2016-01-01

    Here, we report on the use of electrochemical methods for the detection of volatiles fatty acids (VFAs), namely acetic acid. We used tetra-tert-butyl phthalocyanine (PcH2-tBu) as the sensing material and investigated its electroanalytical properties by means of cyclic voltammetry (CV) and square wave voltammetry (SWV). To realize the electrochemical sensing system, the PcH2-tBu has been dropcast-deposited on carbon (C) orgold (Au)screen-printed electrodes (SPEs) and characterized by cyclic voltammetry and scanning electron microscopy (SEM). The SEM analysis reveals that the PcH2-tBu forms mainly aggregates on the SPEs. The modified electrodes are used for the detection of acetic acid and present a linear current increase when the acetic acid concentration increases. The Cmodified electrode presents a limit of detection (LOD) of 25.77 mM in the range of 100 mM–400 mM, while the Aumodified electrode presents an LOD averaging 40.89 mM in the range of 50 mM–300 mM. When the experiment is realized in a buffered condition, theCmodified electrode presents a lower LOD, which averagesthe 7.76 mM. A pronounced signal decay attributed to an electrode alteration is observed in the case of the gold electrode. This electrode alteration severely affects the coating stability. This alteration is less perceptible in the case of the carbon electrode. PMID:27598214

  11. Research-derived insights into surface geochemical hydrocarbon exploration

    USGS Publications Warehouse

    Price, L.C.

    1996-01-01

    Research studies based on foreland basins (mainly in eastern Colorado) examined three surface geochemical exploration (SGE) methods as possible hydrocarbon (HC) exploration techniques. The first method, microbial soil surveying, has high potential as an exploration tool, especially hi development and enhanced recovery operations. Integrative adsorption, the second technique, is not effective as a quantitative SGE method because water, carbon dioxide, nitrous oxide, unsaturated hydrocarbons, and organic compounds are collected by the adsorbent (activated charcoal) much more strongly than covalently bonded microseeping Q-Cs thermogenic HCs. Qualitative comparisons (pattern recognition) of C8+ mass spectra cannot gauge HC gas microseepage that involves only the Q-Cs HCs. The third method, soil cakite surveying, also has no potential as an exploration tool. Soil calcite concentrations had patterns with pronounced areal contrasts, but these patterns had no geometric relationship to surface traces of established or potential production, that is, the patterns were random. Microscopic examination of thousands of soils revealed that soil calcite was an uncrystallized caliche coating soil particles. During its precipitation, caliche captures or occludes any gases, elements, or compounds in its immediate vicinity. Thus, increased signal intensity of some SGE methods should depend on increasing soil calcite concentrations. Analyses substantiate this hypothesis. Because soil calcite has no utility as a surface exploration tool, any surface method that depends on soil calcite has a diminished utility as an SGE tool. Isotopic analyses of soil calcites revealed carbonate carbon ??13C values of -4.0 to +2.07co (indicating a strong influence of atmospheric CO2) as opposed to expected values of-45 to -30%c if the carbonate carbon had originated from microbial oxidation of microseeping HC gases. These analyses confirm a surface origin for this soil calcite (caliche), which is not

  12. Do measures matter? Comparing surface-density-derived and census-tract-derived measures of racial residential segregation

    PubMed Central

    2010-01-01

    Background Racial residential segregation is hypothesized to affect population health by systematically patterning health-relevant exposures and opportunities according to individuals' race or income. Growing interest into the association between residential segregation and health disparities demands more rigorous appraisal of commonly used measures of segregation. Most current studies rely on census tracts as approximations of the local residential environment when calculating segregation indices of either neighborhoods or metropolitan areas. Because census tracts are arbitrary in size and shape, reliance on this geographic scale limits understanding of place-health associations. More flexible, explicitly spatial derivations of traditional segregation indices have been proposed but have not been compared with tract-derived measures in the context of health disparities studies common to social epidemiology, health demography, or medical geography. We compared segregation measured with tract-derived as well as GIS surface-density-derived indices. Measures were compared by region and population size, and segregation measures were linked to birth record to estimate the difference in association between segregation and very preterm birth. Separate analyses focus on metropolitan segregation and on neighborhood segregation. Results Across 231 metropolitan areas, tract-derived and surface-density-derived segregation measures are highly correlated. However overall correlation obscures important differences by region and metropolitan size. In general the discrepancy between measure types is greatest for small metropolitan areas, declining with increasing population size. Discrepancies in measures are greatest in the South, and smallest in Western metropolitan areas. Choice of segregation index changed the magnitude of the measured association between segregation and very preterm birth. For example among black women, the risk ratio for very preterm birth in metropolitan

  13. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    DOE PAGES

    Cui, Chaonan; Han, Jinyu; Zhu, Xinli; ...

    2016-01-16

    In this study, tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react withmore » the hydroxyl, forming a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous Csingle bondO bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the oxide monolayer maybe formed by the reduction, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. The results show that the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of –0.20 V (RHE), lower than that for the latter (–0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product.« less

  14. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    SciTech Connect

    Cui, Chaonan; Han, Jinyu; Zhu, Xinli; Liu, Xiao; Wang, Hua; Mei, Donghai; Ge, Qingfeng

    2016-11-01

    Tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react with the hydroxyl, forming a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous C-O bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the monolayer maybe formed by the reduction of the monolayer, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. However, the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of -0.20 V (RHE), lower than that for the latter (-0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby, providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product. The work was supported in part by National Natural Sciences Foundation of China (Grant #21373148 and #21206117). The High Performance Computing

  15. Functional link between surface low-coordination sites and the electrochemical durability of Pt nanoparticles

    NASA Astrophysics Data System (ADS)

    Chung, Dong Young; Shin, Heejong; Yoo, Ji Mun; Lee, Kug-Seung; Lee, Nam-Suk; Kang, Kisuk; Sung, Yung-Eun

    2016-12-01

    A promising strategy for achieving enhanced catalytic activity involves the use of nanoscale electrocatalysts; however, their low stability remains a major challenge. Among the various performance-degradation mechanisms, atomic dissolution is known to cause severe nanoparticle deactivation. To date, the factors influencing these catalysts' durability are not understood. Herein, we assess the role of low-coordination surface sites, focusing on the atomic dissolution of Pt nanoparticles. The density of low-coordination sites was finely controlled, and no significant size change occurred. Based on our findings, we suggest that the initial low-coordination sites trigger metal dissolution, which subsequently accelerates Pt dissolution. We believe that controlling the surface coordination number can open new routes for the design of highly durable nanoscale electrocatalysts.

  16. Electrode for electrochemical cell

    DOEpatents

    Kaun, T.D.; Nelson, P.A.; Miller, W.E.

    1980-05-09

    An electrode structure for a secondary electrochemical cell includes an outer enclosure defining a compartment containing electrochemical active material. The enclosure includes a rigid electrically conductive metal sheet with perforated openings over major side surfaces. The enclosure can be assembled as first and second trays each with a rigid sheet of perforated electrically conductive metal at major side surfaces and normally extending flanges at parametric margins. The trays can be pressed together with moldable active material between the two to form an expandable electrode. A plurality of positive and negative electrodes thus formed are arranged in an alternating array with porous frangible interelectrode separators within the housing of the secondary electrochemical cell.

  17. Electrode for electrochemical cell

    DOEpatents

    Kaun, Thomas D.; Nelson, Paul A.; Miller, William E.

    1981-01-01

    An electrode structure for a secondary electrochemical cell includes an outer enclosure defining a compartment containing electrochemical active material. The enclosure includes a rigid electrically conductive metal sheet with perforated openings over major side surfaces. The enclosure can be assembled as first and second trays each with a rigid sheet of perforated electrically conductive metal at major side surfaces and normally extending flanges at parametric margins. The trays can be pressed together with moldable active material between the two to form an expandable electrode. A plurality of positive and negative electrodes thus formed are arranged in an alternating array with porous frangible interelectrode separators within the housing of the secondary electrochemical cell.

  18. Electrochemical behavior of a typical redox mediator on a modified electrode surface: Experiment and computer simulations

    NASA Astrophysics Data System (ADS)

    Gavilán Arriazu, E. M.; Paz Zanini, Verónica I.; Gulotta, Florencia A.; Araujo, Virginia M.; Pinto, O. A.

    2017-04-01

    This paper describes the study of a redox species electrosorption on a modified electrode by experimental measurements and computer simulation. The propose model is based on the fact that charges are transferred to the electrode when an electroactive species is adsorbed on its surface. The electrode surface is modified by the irreversible adsorption of a non-electroactive species, which blocks a percentage of the adsorption sites. Hence, the electroactive species can only be adsorbed on the surface vacancies, and, when this phenomenon occurs, interact laterally with the non-electroactive one. Lattice-gas models and Monte Carlo simulations in the Gran Canonical Ensemble are used. The analysis conducted is based on the study of adsorption isotherms and voltammograms, for several values of energies and adsorption degrees of the non-electroactive species. In the case of experimental measurements, an artificial clay (Laponite®) represents the non-electroactive species while the redox probe Fe(CN)64- is the electroactive one. The results obtained by the proposed model are compared with experimental voltammograms.

  19. The surface and electrochemical analysis of permanganate based conversion coating on alclad and unclad 2024 alloy

    NASA Astrophysics Data System (ADS)

    Yoganandan, G.; Balaraju, J. N.; William Grips, V. K.

    2012-09-01

    In the present investigation permanganate based conversion coating (PCC) was developed on AA 2024 alloy using alkaline bath containing Mn/Mo oxyanions. Conversion coating was formed on alclad (APCC) and unclad (UPCC) aluminium alloys by simple immersion method. Surface morphology of the APCC and UPCC specimens exhibited smooth and mud-crack patterns respectively. Elemental analysis showed the presence of higher amounts of Mn (5-6 wt.%) and Mo (0.3 wt.%) on UPCC. Raman and XPS analysis showed the presence of compounds such as MnOx (Mn3O4 and Mn2O3), MnO2, KMnO4, MoOx, MoO2, MoO3/polymolybdate on both coating surfaces. The corrosion current density (icorr) values obtained for both coated surfaces were less than 1 μA/cm2. However, APCC specimen showed the lowest icorr value of about 0.05 μA/cm2 after 168 h of immersion in 3.5% NaCl. EIS studies revealed the higher charge transfer resistance (Rct) values for APCC specimen after 1 and 168 h immersion compared to UPCC. Coated specimens were also tested by continuous salt spray exposure (ASTM B117) with and without cross-hatch mark ('X') for about 750 h. Coating discoloration along with the presence of few corrosion products had been noticed on UPCC specimen after continuous salt spray exposure.

  20. Surface wettability of TiO2 nanotube arrays prepared by electrochemical anodization

    NASA Astrophysics Data System (ADS)

    Liu, Guohua; Du, Kang; Wang, Kaiying

    2016-12-01

    This work reports structural engineering and wettability of titania nanotube arrays (TNTs). The nanotube diameter and thickness of TNT layer increase with increasing of applied voltage from 20 to 40, 60 and 80 V, and the diameter has no relevance to extending anodic duration. The fabricated TNTs are 30-190 nm inner diameter and 5-40 mm height. 10 mL water droplets are applied to define wettability of the TNTs by measuring contact angles. Hydrophilicity is enhanced with increasing diameter of TNTs as well as over-etching occurring on the surface. Large diameter tubes and capillary force provide more space and power for liquid to penetration. The contact angle reduces from 35° to 2° with the tube diameter increasing from 30 to 190 nm. Bare Ti foil is inherently hydrophobic with approximately 90° contact angle. The as-prepared TNTs are hydrophilic with contact angle of 24°, and annealing further improves this property to a contact angle of 13°. The bottom of TNTs shows superhydrophilic due to hydroxide compounds existed on the surface. The metal substrate with tube footprint left presents hydrophobic with contact angle of 68°, which is lower than the bare one. It is believed that wettability on the surface of TNTs is dependent on their morphology and chemical composition.

  1. Bulk Surface Momentum Parameters for Satellite-Derived Vegetation Fields

    NASA Technical Reports Server (NTRS)

    Jasinski, Michael F.; Borak, Jordan; Crago, Richard

    2005-01-01

    The bulk aerodynamic parameters associated with the absorption of surface momentum by vegetated landscapes are theoretically estimated within the context of Raupach's roughness sublayer formulation. The parameters include the bulk plant drag coefficient, maximum u*/U(sub h), sheltering coefficient, and canopy area density at onset of sheltering. Parameters are estimated for the four principal IGBP land cover classes within the U.S. Southern Great Plains: evergreen needleleaf forests, grasslands, croplands, and open shrublands. The estimation approach applies the Method of Moments to roughness data from several international field experiments and other published sources. The results provide the necessary land surface parameters for satellite-based estimation of momentum aerodynamic roughness length and zero-plane displacement height for seasonally variable vegetation fields employed in most terrestrial and atmospheric simulation models used today. Construction of sample displacement and roughness maps over the Southern United States using MODIS land products demonstrates the potential of this approach for regional to global applications.

  2. Satellite-Derived Sea Surface Temperature: Workshop-2

    NASA Technical Reports Server (NTRS)

    Njoku, E. G.

    1984-01-01

    Global accuracies and error characteristics of presently orbiting satellite sensors are examined. The workshops are intended to lead to a better understanding of present capabilities for sea surface temperature measurement and to improve measurement concepts for the future. Data from the Advanced Very High Resolution Radiometer AVHRR and Scanning Multichannel Microwave Radiometer is emphasized. Some data from the High Resolution Infrared Sounder HIRS and AVHRR are also examined. Comparisons of satellite data with ship and eXpendable BathyThermograph XBT measurement show standard deviations in the range 0.5 to 1.3 C with biases of less than 0.4 C, depending on the sensor, ocean region, and spatial/temporal averaging. The Sea Surface Temperature SST anomaly maps show good agreement in some cases, but a number of sensor related problems are identified.

  3. Binding, Electrochemical Activation and Cleavage of DNA by Cobalt(II)tetrakis-N-Methylpyridyl Porphyrin and its β-Pyrrole Brominated Derivative

    PubMed Central

    Yellappa, Shivaraj; Seetharamappa, Jaldappagari; Rogers, Lisa M.; Chitta, Raghu; Singhal, Ram P.; D’Souza, Francis

    2008-01-01

    The binding of nucleic acids by water soluble cobalt(II) tetrakis-N-methylpyridyl porphyrin, (TMPyP)Co and its highly electron deficient derivative, cobalt(II) tetrakis-N-methyl pyridyl-β-octabromoporphyrin, (Br8TMPyP)Co was investigated by UV-visible absorption, circular dichroism (CD), electrochemical and gel electrophoresis methods. The changes of the absorption spectra during the titration of these complexes with polynucleotides revealed a shift in the absorption maxima and a hypochromicity of the porphyrin Soret bands. The intrinsic binding constants were found to be in the range of 105 – 106 M−1. These values were higher for more electron deficient (Br8TMPyP)Co. Induced CD bands were noticed in the Soret region of the complexes due to the interaction of these complexes with different polynucleotides and an analysis of the CD spectra supported mainly external mode of binding. Electrochemical studies revealed the cleavage of polynucleotide by (TMPyP)Co and (Br8TMPyP)Co in the presence of oxygen preferentially at the A-T base pair region. Gel electrophoresis experiments further supported the cleavage of nucleic acids. The results indicate that the β-pyrrole brominated porphyrin, (Br8TMPyP)Co binds strongly and cleaves nucleic acids efficiently as compared to (TMPyP)Co. This electrolytic procedure offers a unique tool in biotechnology for cleaving double-stranded DNA with specificity at the A-T regions. PMID:17105219

  4. Effect of surface treatments on anodic oxide film growth and electrochemical properties of tantalum used for biomedical applications.

    PubMed

    Silva, R A; Silva, I P; Rondot, B

    2006-07-01

    Self-expandable nitinol (nickel-titanium) alloys and 316L stainless steel are the most commonly used materials in the production of coronary stents. However, tantalum (Ta) has already been used to make stents for endovascular surgery and may constitute an alternative to other materials because of its better electrochemical performance, namely its higher corrosion resistance, as well as its radio-opacity. The characterization of wet polished, chemically polished, wet polished anodized, and chemically polished anodized Ta electrodes has been performed in a 0.15 M NaCl solution (simulated body fluid) using Ucorr = f(t) measurements, anodic polarizations, capacity measurements, anodic oxidations, and atomic force microscopy (AFM) imaging. Anodic polarization curves have shown that the abnormal current density peak with a maximum value around 1.65 V (critical applied potential, Uc) disappeared for the anodized electrodes indicating a probable relationship between the surface states and the film growth. These results are confirmed by capacity measurements. The behavior of wet polished and chemically polished electrodes during anodic oxidations seemingly indicated that for these particular treatments the film growth is different. The AFM images and roughness measurements have shown that chemical polishing produced smoother electrodes, a fact probably related to the differences in film growth.

  5. Efficient Electrochemical and Photoelectrochemical H2 Production from Water by a Cobalt Dithiolene One-Dimensional Metal-Organic Surface.

    PubMed

    Downes, Courtney A; Marinescu, Smaranda C

    2015-11-04

    Solar-driven hydrogen evolution from water has emerged as an important methodology for the storage of renewable energy in chemical bonds. Efficient and practical clean-energy devices for electrochemical or photoelectrochemical splitting of water require the immobilization of stable and active hydrogen-evolving catalysts onto electrode or photocathode materials, which remains a significant challenge. Here we show that cobalt(II) reacts with benzene-1,2,4,5-tetrathiol in the presence of base to form a cobalt dithiolene polymer 1. The generated polymer is immobilized onto glassy carbon electrodes (GCE) to generate a metal-organic surface (MOS 1|GCE), which displays efficient H2-evolving activity and stability in acidic aqueous solutions. Moreover, the generated polymer is integrated with planar p-type Si to generate very efficient photocathode materials (MOS 1|Si) for solar-driven hydrogen production from water. Photocurrents up to 3.8 mA/cm(2) at 0 V vs RHE were achieved under simulated 1 Sun illumination. MOS 1|Si photocathodes operate at potentials 550 mV more positive than MOS 1|GCE cathodes to reach the same activity for H2 evolution from water (1 mA/cm(2)).

  6. Electrochemical and surface analyses of nanostructured Ti-24Nb-4Zr-8Sn alloys in simulated body solution.

    PubMed

    Li, J; Li, S J; Hao, Y L; Huang, H H; Bai, Y; Hao, Y Q; Guo, Z; Xue, J Q; Yang, R

    2014-06-01

    The use of nanostructuring to improve the stability of passive thin films on biomaterials can enhance their effectiveness in corrosion resistance and reduce the release of ions. The thickness of the ultrathin films that cover Ti and Ti alloys (only several nanometers) has prevented researchers from establishing systematic methods for their characterization. This study employed a multifunctional biomedical titanium alloy Ti-24Nb-4Zr-8Sn (wt.%) as a model material. Coarse-grained (CG) and nanostructured (NS) alloys were analyzed in 0.9% NaCl solution at 37°C. To reveal the details of the passive film, a method of sample preparation producing a passive layer suitable for transmission electron microscope analysis was developed. Electrochemical corrosion behavior was evaluated by potentiodynamic polarization tests and Mott-Schottky measurements. Surface depth chemical profile and morphology evolution were performed by X-ray photoelectron spectroscopy and in situ atomic force microscopy, respectively. A mechanism was proposed on the basis of the point defect model to compare the corrosion resistance of the passive film on NS and CG alloys. Results showed that the protective amorphous film on NS alloy is thicker, denser and more homogeneous with fewer defects than that on CG alloy. The film on NS alloy contains more oxygen and corrosion-resistant elements (Ti and Nb), as well as their suboxides, compared with the film on CG alloy. These characteristics can be attributed to the rapid, uniform growth of the passive film facilitated by nanostructuring.

  7. Small Gold Nanoparticles Interfaced to Electrodes through Molecular Linkers: A Platform to Enhance Electron Transfer and Increase Electrochemically Active Surface Area.

    PubMed

    Young, Samantha L; Kellon, Jaclyn E; Hutchison, James E

    2016-10-17

    For the smallest nanostructures (<5 nm), small changes in structure can lead to significant changes in properties and reactivity. In the case of nanoparticle (NP)-functionalized electrodes, NP structure and composition, and the nature of the NP-electrode interface have a strong influence upon electrochemical properties that are critical in applications such as amperometric sensing, photocatalysis and electrocatalysis. Existing methods to fabricate NP-functionalized electrodes do not allow for precise control over all these variables, especially the NP-electrode interface, making it difficult to understand and predict how structural changes influence NP activity. We investigated the electrochemical properties of small (dcore < 2.5 nm) gold nanoparticles (AuNPs) on boron doped diamond electrodes using three different electrode fabrication techniques with varying degrees of nanoparticle-electrode interface definition. Two methods to attach AuNPs to the electrode through a covalently bound molecular linker were developed and compared to NP-functionalized electrodes fabricated using solution deposition methods (drop-casting and physiadsorption of a monolayer). In each case, a ferrocene redox probe was tethered to the AuNP surface to evaluate electron transfer through the AuNPs. The AuNPs that were molecularly interfaced with the electrode exhibited nearly ideal, reproducible electrochemical behavior with narrow redox peaks and small peak separations, whereas the solution deposited NPs had broader redox peaks with large peak separations. These data suggest that the molecular tether facilitates AuNP-mediated electron transfer. Interestingly, the molecularly tethered NPs also had significantly more electrochemically active surface area than the solution deposited NPs. The enhanced electrochemical behavior of the molecularly interfaced NPs demonstrates the significant influence of the interface on NP-mediated electron transfer and suggests that similar modified electrodes

  8. Electrochemical performance of LiCoO 2 cathodes by surface modification using lanthanum aluminum garnet

    NASA Astrophysics Data System (ADS)

    Lu, Cheng-Zhang; Chen, Jin-Ming; Cho, Yung-Da; Hsu, Wen-Hsiang; Muralidharan, P.; Fey, George Ting-Kuo

    LiCoO 2 particles were coated with various wt.% of lanthanum aluminum garnets (3LaAlO 3:Al 2O 3) by an in situ sol-gel process, followed by calcination at 1123 K for 12 h in air. X-ray diffraction (XRD) patterns confirmed the formation of a 3LaAlO 3:Al 2O 3 compound and the in situ sol-gel process synthesized 3LaAlO 3:Al 2O 3-coated LiCoO 2 was a single-phase hexagonal α-NaFeO 2-type structure of the core material without any modification. Scanning electron microscope (SEM) images revealed a modification of the surface of the cathode particles. Transmission electron microscope (TEM) images exposed that the surface of the core material was coated with a uniform compact layer of 3LaAlO 3:Al 2O 3, which had an average thickness of 40 nm. Galvanostatic cycling studies demonstrated that the 1.0 wt.% 3LaAlO 3:Al 2O 3-coated LiCoO 2 cathode showed excellent cycle stability of 182 cycles, which was much higher than the 38 cycles sustained by the pristine LiCoO 2 cathode material when it was charged at 4.4 V.

  9. Fabrication of a Horizontal and a Vertical Large Surface Area Nanogap Electrochemical Sensor

    PubMed Central

    Hammond, Jules L.; Rosamond, Mark C.; Sivaraya, Siva; Marken, Frank; Estrela, Pedro

    2016-01-01

    Nanogap sensors have a wide range of applications as they can provide accurate direct detection of biomolecules through impedimetric or amperometric signals. Signal response from nanogap sensors is dependent on both the electrode spacing and surface area. However, creating large surface area nanogap sensors presents several challenges during fabrication. We show two different approaches to achieve both horizontal and vertical coplanar nanogap geometries. In the first method we use electron-beam lithography (EBL) to pattern an 11 mm long serpentine nanogap (215 nm) between two electrodes. For the second method we use inductively-coupled plasma (ICP) reactive ion etching (RIE) to create a channel in a silicon substrate, optically pattern a buried 1.0 mm × 1.5 mm electrode before anodically bonding a second identical electrode, patterned on glass, directly above. The devices have a wide range of applicability in different sensing techniques with the large area nanogaps presenting advantages over other devices of the same family. As a case study we explore the detection of peptide nucleic acid (PNA)−DNA binding events using dielectric spectroscopy with the horizontal coplanar device. PMID:27983655

  10. Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes**

    PubMed Central

    Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

    2015-01-01

    In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6Sr0.4FeO3−δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe0 on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. PMID:25557533

  11. Transparent, durable and thermally stable PDMS-derived superhydrophobic surfaces

    NASA Astrophysics Data System (ADS)

    Liu, Xiaojiang; Xu, Yang; Ben, Keyang; Chen, Zao; Wang, Yan; Guan, Zisheng

    2015-06-01

    We reported a novel, simple, modification-free process for the preparation of transparent superhydrophobic surfaces by calcining candle-soot-coated polydimethylsiloxane (PDMS) films. Though a calcination process, a candle soot template was gradually removed while robust fibrous and network structures were created on glass. Owing to these structures, the glass substrates were durable and highly transparent with an average transmittance (400-800 nm) of 89.50%, very closed to the bare glass slides (89.70%). These substrates exhibited a water contact angle (WCA) of 163° and a sliding angle (SA) of ∼1°. Importantly, the superhydrophobicity of these surfaces can thermally recover after oil-contamination due to their high thermal stability below 500 °C. Based on these, superhydrophobic fiberglass cotton was also prepared for optimized oil-water separation and air filtration. This method is suitable for large-scale production because it uses inexpensive and environmentally friendly materials and gets rids of sophisticated equipment, special atmosphere and harsh operations.

  12. Adsorption of Amlodipine at the Surface of Tosyl─Carbon Nanoparticles for Electrochemical Sensing

    PubMed Central

    Amiri, Mandana; Imanzade, Hamideh

    2016-01-01

    The adsorption processes of amlodipine onto hydrophilic carbon nanoparticles (Emperor 2000TM) are investigated. The significant increase in voltammetric responses for pre-adsorbed amlodipine compared with those for solution confirms high affinity of amlodipine to carbon nanoparticles (possibly due to π-π stacking interaction between aromatic rings of amlodipine and surface-sulfonated carbon nanoparticles). To obtain the optimum of adsorption conditions, the effects of pH, agitation rate, and adsorption time are investigated. Under differential pulse voltammetry conditions, the peak current for the oxidation of amlodipine shows two linear relationships with concentration in the range from 1000 μM to 10.0 μM and 10.0 μM to 10.0 nM. The limit of detection is estimated to be 1.0 nM. Determination of amlodipine in real samples such as human serum and commercial tablets is demonstrated. PMID:27980564

  13. Aggregation of Individual Sensing Units for Signal Accumulation: Conversion of Liquid-Phase Colorimetric Assay into Enhanced Surface-Tethered Electrochemical Analysis.

    PubMed

    Wei, Tianxiang; Dong, Tingting; Wang, Zhaoyin; Bao, Jianchun; Tu, Wenwen; Dai, Zhihui

    2015-07-22

    A novel concept is proposed for converting liquid-phase colorimetric assay into enhanced surface-tethered electrochemical analysis, which is based on the analyte-induced formation of a network architecture of metal nanoparticles (MNs). In a proof-of-concept trial, thymine-functionalized silver nanoparticle (Ag-T) is designed as the sensing unit for Hg(2+) determination. Through a specific T-Hg(2+)-T coordination, the validation system based on functionalized sensing units not only can perform well in a colorimetric Hg(2+) assay, but also can be developed into a more sensitive and stable electrochemical Hg(2+) sensor. In electrochemical analysis, the simple principle of analyte-induced aggregation of MNs can be used as a dual signal amplification strategy for significantly improving the detection sensitivity. More importantly, those numerous and diverse colorimetric assays that rely on the target-induced aggregation of MNs can be augmented to satisfy the ambitious demands of sensitive analysis by converting them into electrochemical assays via this approach.

  14. Global fields of soil moisture and land surface evapotranspiration derived from observed precipitation and surface air temperature

    NASA Technical Reports Server (NTRS)

    Mintz, Y.; Walker, G. K.

    1993-01-01

    The global fields of normal monthly soil moisture and land surface evapotranspiration are derived with a simple water budget model that has precipitation and potential evapotranspiration as inputs. The precipitation is observed and the potential evapotranspiration is derived from the observed surface air temperature with the empirical regression equation of Thornthwaite (1954). It is shown that at locations where the net surface radiation flux has been measured, the potential evapotranspiration given by the Thornthwaite equation is in good agreement with those obtained with the radiation-based formulations of Priestley and Taylor (1972), Penman (1948), and Budyko (1956-1974), and this provides the justification for the use of the Thornthwaite equation. After deriving the global fields of soil moisture and evapotranspiration, the assumption is made that the potential evapotranspiration given by the Thornthwaite equation and by the Priestley-Taylor equation will everywhere be about the same; the inverse of the Priestley-Taylor equation is used to obtain the normal monthly global fields of net surface radiation flux minus ground heat storage. This and the derived evapotranspiration are then used in the equation for energy conservation at the surface of the earth to obtain the global fields of normal monthly sensible heat flux from the land surface to the atmosphere.

  15. Satellite-Derived Sea Surface Temperature: Workshop 3

    NASA Technical Reports Server (NTRS)

    1985-01-01

    This is the third of a series of three workshops, sponsored by the National Aeronautics and Space Administration, to investigate the state of the art in global sea surface temperature measurements from space. Three workshops were necessary to process and analyze sufficient data from which to draw conclusions on the accuracy and reliability of the satellite measurements. In this workshop, the final two (out of a total of four) months of satellite and in situ data chosen for study were processed and evaluated. Results from the AVHRR, HIRS, SMMR, and VAS sensors, in comparison with in situ data from ships, XBTs, and buoys, confirmed satellite rms accuracies in the 0.5 to 1.0 C range, but with variable biases. These accuracies may degrade under adverse conditions for specific sensors. A variety of color maps, plots, and statistical tables are provided for detailed study of the individual sensor SST measurements.

  16. High surface area electrodes in ionic polymer transducers: Numerical and experimental investigations of the electro-chemical behavior

    NASA Astrophysics Data System (ADS)

    Akle, Barbar J.; Habchi, Wassim; Wallmersperger, Thomas; Akle, Etienne J.; Leo, Donald J.

    2011-04-01

    Ionomeric polymer transducer (IPT) is an electroactive polymer that has received considerable attention due to its ability to generate large bending strain (>5%) and moderate stress at low applied voltages (±2 V). Ionic polymer transducers consist of an ionomer, usually Nafion, sandwiched between two electrically conductive electrodes. A novel fabrication technique denoted as the direct assembly process (DAP) enabled controlled electrode architecture in ionic polymer transducers. A DAP built transducer consists of two high surface area electrodes made of electrically conducting particles uniformly distributed in an ionomer matrix sandwiching an ionomer membrane. The purpose of this paper is to investigate and simulate the effect of these high surface area particles on the electro-chemical response of an IPT. Theoretical investigations as well as experimental verifications are performed. The model used consists of a convection-diffusion equation describing the chemical field as well as a Poisson equation describing the electrical field. The two-dimensional model incorporates highly conductive particles randomly distributed in the electrode area. Traditionally, these kinds of electrodes were simulated with boundary conditions representing flat electrodes with a large dielectric permittivity at the polymer boundary. This model enables the design of electrodes with complicated geometrical patterns. In the experimental section, several transducers are fabricated using the DAP process on Nafion 117 membranes. The architecture of the high surface area electrodes in these samples is varied. The concentration of the high surface area RuO2 particles is varied from 30 vol% up to 60 vol% at a fixed thickness of 30 μm, while the overall thickness of the electrode is varied from 10 μm up to 40 μm at a fixed concentration of 45%. The flux and charge accumulation in the materials are measured experimentally and compared to the results of the numerical simulations. Trends of

  17. Electrospun lignin-derived carbon nanofiber mats surface-decorated with MnO2 nanowhiskers as binder-free supercapacitor electrodes with high performance

    NASA Astrophysics Data System (ADS)

    Ma, Xiaojing; Kolla, Praveen; Zhao, Yong; Smirnova, Alevtina L.; Fong, Hao

    2016-09-01

    The aim of this study is to explore innovative materials for the development of next-generation supercapacitor electrodes. The hypothesis is that, upon the surface-decoration with appropriate amount of MnO2 nanowhiskers, freestanding and highly graphitic electrospun carbon nanofiber (ECNF) mats (with fiber diameters of ∼200 nm and BET specific surface areas of ∼583 m2 g-1) derived from a natural product of lignin would be binder-free supercapacitor electrodes with high performance. To test the hypothesis, the ECNF mats have been prepared first; thereafter, the acquired ECNF mats have been surface-decorated with varied amounts of MnO2 nanowhiskers to prepare three types of ECNF/MnO2 mats. The morphological and structural properties of ECNF and ECNF/MnO2 mats are characterized by SEM, TEM and XRD, the weight percentages of MnO2 nanowhiskers in three ECNF/MnO2 mats are determined by thermal gravimetric analysis; while the electrochemical performance of each mat/electrode is evaluated by cyclic voltammetry, galvanostatic charge/discharge method, and electrochemical impedance spectroscopy. This study reveals that, all of the three ECNF/MnO2 mats/electrodes have significantly enhanced electrochemical performances compared to the ECNF mat/electrode; while the ECNF/MnO2 (1:1) mat/electrode exhibits the highest gravimetric capacitance of 83.3 F g-1, energy density of 84.3 W h kg-1, and power density of 5.72 kW kg-1.

  18. Structural and electrochemical characterization and surface modification of layered solid solution oxide cathodes of lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wu, Yan

    Lithium ion batteries are widely used to power portable electronic devices such as cell phones and laptop computers due to their high energy density. However, the currently used layered LiCoO2 cathode could deliver only 50 % of its theoretical capacity in practical lithium ion cells (140 mAh/g) due to the chemical and structural instabilities at deep charge with (1-x) < 0.5 in Li1-xCoO2. Also, cobalt is relatively expensive and toxic. These difficulties have generated enormous interest in alternative cathode hosts. In this regard, solid solutions between layered Li[Li1/3Mn2/3]O2 (commonly designated as Li2MnO3) and LiMO2 (M = Mn, Ni, Co)) have become appealing as some of them exhibit much higher capacity (˜ 250 mAh/g on charging to 4.8 V) with lower cost and better safety compared to LiCoO 2. This dissertation investigates the (1-z) Li[Li1/3Mn 2/3]O2 - (z) Li[Mn0.5-yNi0.5-yCo 2y]O2 (y = 1/12, 1/6 and 1/3 and 0.25 = z = 0.75) layered oxide cathodes, which belong to a solid solution series between layered Li[Li 1/3Mn2/3]O2 and Li[Mn0.5-yNi0.5-y Co2y]O2, with an aim to develop a better understanding of the charge-discharge mechanisms and optimize the electrochemical performance of these materials. To accomplish this, the structural and electrochemical characterization of the (1- z) Li[Li1/3Mn2/3]O2 - (z) Li[Mn 0.5-yNi0.5-yCo2y]O2 cathodes is carried out. It is found that the amount of oxygen loss is related to the lithium content in the transition metal layer, and the Co and Mn4+ contents play a role in influencing the electrochemical behavior. In addition, the chemically delithiated samples are found to transform to O1 or P3 structure with a vanishing of the superlattice reflections arising from cationic ordering in the transition metal layer due to the incorporation of protons from the chemical delithiation medium, while the electrochemically charged samples retain the initial O3 structure. These layered solid solution oxides exhibit high irreversible capacity (IRC

  19. Tunable Surface Structuration of Silicon by Metal Assisted Chemical Etching with Pt Nanoparticles under Electrochemical Bias.

    PubMed

    Torralba, Encarnación; Le Gall, Sylvain; Lachaume, Raphaël; Magnin, Vincent; Harari, Joseph; Halbwax, Mathieu; Vilcot, Jean-Pierre; Cachet-Vivier, Christine; Bastide, Stéphane

    2016-11-16

    An in-depth study of metal assisted chemical etching (MACE) of p-type c-Si in HF/H2O2 aqueous solutions using Pt nanoparticles as catalysts is presented. Combination of cyclic voltammetry, open circuit measurements, chronoamperometry, impedance spectroscopy, and 2D band bending modeling of the metal/semiconductor/electrolyte interfaces at the nanoscale and under different etching conditions allows gaining physical insights into this system. Additionally, in an attempt to mimic the etching conditions, the modeling has been performed with a positively biased nanoparticle buried in the Si substrate. Following these findings, the application of an external polarization during etching is introduced as a novel efficient approach for achieving straightforward control of the pore morphology by acting upon the band bending at the Si/electrolyte junction. In this way, nanostructures ranging from straight mesopores to cone-shaped macropores are obtained as the Si sample is biased from negative to positive potentials. Remarkably, macroscopic cone-shaped pores in the 1-5 μm size range with a high aspect ratio (L/W ∼ 1.6) are obtained by this method. This morphology leads to a reduction of the surface reflectance below 5% over the entire VIS-NIR domain, which outperforms macrostructures made by state of the art texturization techniques for Si solar cells.

  20. Positive pressure ventilation during anesthesia in dogs: Assessment of surface area derived tidal volume.

    PubMed

    Dyson, Doris H

    2012-01-01

    The purpose of this study was to assess the use of surface area derived tidal volume in anesthetized ventilated dogs (n = 71, random assignment) compared to settings by experienced personnel. There was no significant difference (P = 0.1030) between methods (p(a)CO(2) of 43.1 ± 7 mmHg and 39.8 ± 7 mmHg, respectively). Surface area derived tidal volume can achieve satisfactory ventilation.

  1. Evaluation of orthomosics and digital surface models derived from aerial imagery for crop mapping

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Orthomosics derived from aerial imagery acquired by consumer-grade cameras have been used for crop mapping. However, digital surface models (DSM) derived from aerial imagery have not been evaluated for this application. In this study, a novel method was proposed to extract crop height from DSM and t...

  2. Satellite Derived Earth Surface Temperatures: a Crop Assessment Tool.

    NASA Astrophysics Data System (ADS)

    Crosiar, Christy Lynn

    The data for this research consist of the following: 23 days of NOAA/AVHRR satellite data; AgRISTARS enumerator data (or ground truth data) for 26 counties in three midwestern states (Iowa, Nebraska and North Dakota) and radiosonde observations for nine upper air stations, producing an 8 state coverage. The objectives of this research are threefold: (1) to develop a regression model to estimate maximum shelter temperature, (2) to develop a method to assess crop conditions and (3) to determine the variability within a scan line due to changes in optical depth and/or scan angle. The regression model uses three independent variables derived from satellite data to predict maximum shelter temperature. The first independent variable is the satellite's first estimate of temperature, the channel 4 effective temperature. The second independent variable is the difference in the amount of radiation received by the satellite's two thermal channels (4 and 5) serving as a measure of the water vapor in the atmosphere. The third independent variable, path length, uses the pixel position within the scan line to calculate the viewing angle from nadir. This approach resulted in a good R^2 of.65. Three reasons to explain why this R ^2 is not stronger are as follows: (1) a known temperature difference between satellite and shelter temperature, (2) unregistered satellite data--the latitude and longitude of the satellite data are not the location of the shelter and (3) comparison of an area averaged temperature (satellite data) to a point source (shelter) measurement are two different values. The second objective is using satellite data, during the heading and flowering period, combined with the ground truth data or the enumerator data obtained through the AgRISTARS program to determine crop stress. Using two regression models, two satellite temperature indices are used as predictors of a ratio in yield. Statistically significant relationships exist for soybeans and sunflowers. The third

  3. Sampling Errors in Satellite-derived Infrared Sea Surface Temperatures

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Minnett, P. J.

    2014-12-01

    Sea Surface Temperature (SST) measured from satellites has been playing a crucial role in understanding geophysical phenomena. Generating SST Climate Data Records (CDRs) is considered to be the one that imposes the most stringent requirements on data accuracy. For infrared SSTs, sampling uncertainties caused by cloud presence and persistence generate errors. In addition, for sensors with narrow swaths, the swath gap will act as another sampling error source. This study is concerned with quantifying and understanding such sampling errors, which are important for SST CDR generation and for a wide range of satellite SST users. In order to quantify these errors, a reference Level 4 SST field (Multi-scale Ultra-high Resolution SST) is sampled by using realistic swath and cloud masks of Moderate Resolution Imaging Spectroradiometer (MODIS) and Advanced Along Track Scanning Radiometer (AATSR). Global and regional SST uncertainties are studied by assessing the sampling error at different temporal and spatial resolutions (7 spatial resolutions from 4 kilometers to 5.0° at the equator and 5 temporal resolutions from daily to monthly). Global annual and seasonal mean sampling errors are large in the high latitude regions, especially the Arctic, and have geographical distributions that are most likely related to stratus clouds occurrence and persistence. The region between 30°N and 30°S has smaller errors compared to higher latitudes, except for the Tropical Instability Wave area, where persistent negative errors are found. Important differences in sampling errors are also found between the broad and narrow swath scan patterns and between day and night fields. This is the first time that realistic magnitudes of the sampling errors are quantified. Future improvement in the accuracy of SST products will benefit from this quantification.

  4. Derivation of Improved Surface and TOA Broadband Fluxes Using CERES-derived Narrowband-to-Broadband Coefficients

    NASA Technical Reports Server (NTRS)

    Khaiyer, Mandana M.; Doelling, David R.; Chan, Pui K.; Nordeen, MIchele L.; Palikonda, Rabindra; Yi, Yuhong; Minnis, Patrick

    2006-01-01

    Satellites can provide global coverage of a number of climatically important radiative parameters, including broadband (BB) shortwave (SW) and longwave (LW) fluxes at the top of the atmosphere (TOA) and surface. These parameters can be estimated from narrowband (NB) Geostationary Operational Environmental Satellite (GOES) data, but their accuracy is highly dependent on the validity of the narrowband-to-broadband (NB-BB) conversion formulas that are used to convert the NB fluxes to broadband values. The formula coefficients have historically been derived by regressing matched polarorbiting satellite BB fluxes or radiances with their NB counterparts from GOES (e.g., Minnis et al., 1984). More recently, the coefficients have been based on matched Earth Radiation Budget Experiment (ERBE) and GOES-6 data (Minnis and Smith, 1998). The Clouds and the Earth's Radiant Energy Budget (CERES see Wielicki et al. 1998)) project has recently developed much improved Angular Distribution Models (ADM; Loeb et al., 2003) and has higher resolution data compared to ERBE. A limited set of coefficients was also derived from matched GOES-8 and CERES data taken on Topical Rainfall Measuring Mission (TRMM) satellite (Chakrapani et al., 2003; Doelling et al., 2003). The NB-BB coefficients derived from CERES and the GOES suite should yield more accurate BB fluxes than from ERBE, but are limited spatially and seasonally. With CERES data taken from Terra and Aqua, it is now possible to derive more reliable NB-BB coefficients for any given area. Better TOA fluxes should translate to improved surface radiation fluxes derived using various algorithms. As part of an ongoing effort to provide accurate BB flux estimates for the Atmospheric Radiation Measurement (ARM) Program, this paper documents the derivation of new NB-BB coefficients for the ARM Southern Great Plains (SGP) domain and for the Darwin region of the Tropical Western Pacific (DTWP) domain.

  5. A novel porphyrin derivative and its metal complexes: Electrochemical, photoluminescence, thermal, DNA-binding and superoxide dismutase activity studies

    NASA Astrophysics Data System (ADS)

    Purtaş, Savaş; Köse, Muhammet; Tümer, Ferhan; Tümer, Mehmet; Gölcü, Ayşegül; Ceyhan, Gökhan

    2016-02-01

    In this study, a new porphyrin-Schiff base ligand (L) and its metal complexes (Cu(II), Fe(III), Mn(III), Pt(II) and Zn(II)) were synthesized. The starting material 4-ethyl-2,6-bis(hydroxymethyl)phenol (A) was synthesized from 4-ethylphenol and formaldehyde in the alkaline media. The compound (A) was then oxidized to the 4-ethyl-2,6-diformylphenol (B). The starting compounds (A) and (B) were obtained as single crystals. Structures of the compounds (A) and (B) were determined by the X-ray crytallography technique. The porphyrin ligand (L) and its metal complexes were characterized by the analytical and spectroscopic methods. Electronic, electrochemical and thermal properties of the synthesised compounds were investigated. Superoxide dismutase activities (SOD) of the porphyrin Schiff base complexes were investigated and results were discussed. Additionally, the DNA (fish sperm FSdsDNA) binding studies of the complexes were performed using UV-vis spectroscopy. Competitive studies with ethidium bromide (EB) show that the compounds interact efficiently with DNA through an intercalating way.

  6. Influence of electrolytes (TEABF4 and TEMABF4) on electrochemical performance of graphite oxide derived from needle coke.

    PubMed

    Yang, Sunhye; Kim, Ick-Jun; Choi, In-Sik; Bae, Mi-Kyeong; Kim, Hyun-Soo

    2013-05-01

    The structure of needle coke was changed to graphite oxide structure after oxidation treatment with 70 wt.% of nitric acid and sodium chlorate (NaClO3), and the inter-layer distance of the oxidized needle coke was expanded to 6.9 angstroms. The first charge profile of the oxidized needle coke-cell with 1.2 M TEMABF4/acetonitrile solution displayed that the intercalation of electrolyte ions into the inter-layer occurred at 1.0 V, which value is lower than 1.3 V of the oxidized needle coke-cell with 1.2 M TEABF4/acetonitrile solution. After first charge/discharge, the cell using TEMABF4 electrolyte exhibited smaller electrode resistance of 0.05 omega, and larger specific volume capacitance of 25.5 F/ml at the two-electrode system in the potential range 0-2.5 V than those of the cell using TEABF4 electrolyte. Compared to the TEABF4 electrolyte, better electrochemical performance of the TEMABF4 electrolyte in the oxidized needle coke may be caused by the smaller cation (TEMA+) size and better ion mobility in the nanopores between inter-layers.

  7. Enhanced Electrochemical Performance of Ultracentrifugation-Derived nc-Li3VO4/MWCNT Composites for Hybrid Supercapacitors.

    PubMed

    Iwama, Etsuro; Kawabata, Nozomi; Nishio, Nagare; Kisu, Kazuaki; Miyamoto, Junichi; Naoi, Wako; Rozier, Patrick; Simon, Patrice; Naoi, Katsuhiko

    2016-05-24

    Nanocrystalline Li3VO4 dispersed within multiwalled carbon nanotubes (MWCNTs) was prepared using an ultracentrifugation (uc) process and electrochemically characterized in Li-containing electrolyte. When charged and discharged down to 0.1 V vs Li, the material reached 330 mAh g(-1) (per composite) at an average voltage of about 1.0 V vs Li, with more than 50% capacity retention at a high current density of 20 A g(-1). This current corresponds to a nearly 500C rate (7.2 s) for a porous carbon electrode normally used in electric double-layer capacitor devices (1C = 40 mA g(-1) per activated carbon). The irreversible structure transformation during the first lithiation, assimilated as an activation process, was elucidated by careful investigation of in operando X-ray diffraction and X-ray absorption fine structure measurements. The activation process switches the reaction mechanism from a slow "two-phase" to a fast "solid-solution" in a limited voltage range (2.5-0.76 V vs Li), still keeping the capacity as high as 115 mAh g(-1) (per composite). The uc-Li3VO4 composite operated in this potential range after the activation process allows fast Li(+) intercalation/deintercalation with a small voltage hysteresis, leading to higher energy efficiency. It offers a promising alternative to replace high-rate Li4Ti5O12 electrodes in hybrid supercapacitor applications.

  8. Monomeric mixed cadmium-2,2‧-dipyridylamine complex derived from ferrocenecarboxylic acid: Structural, electrochemical and biological studies

    NASA Astrophysics Data System (ADS)

    Senthilkumar, Kabali; Gopalakrishnan, Mohan; Palanisami, Nallasamy

    2015-09-01

    A mixed Cd(II) complex {[Cd(FcCOO)2(dpyam)(H2O)][Cd(dpyam)2 (H2O)2]·(ClO4)2·CH3OH} (1) (where FcCOO = ferrocenecarboxylic acid and dpyam = 2,2‧-dipyridylamine), has been synthesized and characterized by FT-IR, 1H & 13C NMR, UV-Vis spectroscopy and elemental analysis. The molecular structure of compound 1 has been determined by the single crystal X-ray diffraction technique, which consists of mixed two different cadmium(II) complexes and two uncoordinated perchlorate ions. The crystal packing shows that the compound 1 self-assembled by intermolecular hydrogen bonding via pyridyl N-H⋯O and coordinated water O⋯H-O-H⋯O, to afford the molecule 2D supramolecular network. Compound 1 exhibits high-energy intraligand (π-π∗) fluorescence emission. In electrochemical studies of compound 1 shows negative potential compared with ferrocenecarboxylic acid due to formation of coordination complex with Cd ions. The antibacterial study against the distinct bacterial strains show compound 1 has significant activity.

  9. Monomeric mixed cadmium-2,2'-dipyridylamine complex derived from ferrocenecarboxylic acid: Structural, electrochemical and biological studies.

    PubMed

    Senthilkumar, Kabali; Gopalakrishnan, Mohan; Palanisami, Nallasamy

    2015-09-05

    A mixed Cd(II) complex {[Cd(FcCOO)2(dpyam)(H2O)][Cd(dpyam)2 (H2O)2]·(ClO4)2·CH3OH} (1) (where FcCOO=ferrocenecarboxylic acid and dpyam=2,2'-dipyridylamine), has been synthesized and characterized by FT-IR, (1)H &(13)C NMR, UV-Vis spectroscopy and elemental analysis. The molecular structure of compound 1 has been determined by the single crystal X-ray diffraction technique, which consists of mixed two different cadmium(II) complexes and two uncoordinated perchlorate ions. The crystal packing shows that the compound 1 self-assembled by intermolecular hydrogen bonding via pyridyl N-H⋯O and coordinated water O⋯H-O-H⋯O, to afford the molecule 2D supramolecular network. Compound 1 exhibits high-energy intraligand (π-π(∗)) fluorescence emission. In electrochemical studies of compound 1 shows negative potential compared with ferrocenecarboxylic acid due to formation of coordination complex with Cd ions. The antibacterial study against the distinct bacterial strains show compound 1 has significant activity.

  10. Multi-Functional Surface Engineering for Li-Excess Layered Cathode Material Targeting Excellent Electrochemical and Thermal Safety Properties.

    PubMed

    Bian, Xiaofei; Fu, Qiang; Pang, Qiang; Gao, Yu; Wei, Yingjin; Zou, Bo; Du, Fei; Chen, Gang

    2016-02-10

    The Li(Li(0.18)Ni(0.15)Co(0.15)Mn(0.52))O2 cathode material is modified by a Li4M5O12-like heterostructure and a BiOF surface layer. The interfacial heterostructure triggers the layered-to-Li4M5O12 transformation of the material which is different from the layered-to-LiMn2O4 transformation of the pristine Li(Li(0.18)Ni(0.15)Co(0.15)Mn(0.52))O2. This Li4M5O12-like transformation helps the material to keep high working voltage, long cycle life and excellent rate capability. Mass spectrometry, in situ X-ray diffraction and transmission electron microscope show that the Li4M5O12-like phase prohibits oxygen release from the material bulk at elevated temperatures. In addition, the BiOF coating layer protects the material from harmful side reactions with the electrolyte. These advantages significantly improve the electrochemical performance of Li(Li(0.18)Ni(0.15)Co(0.15)Mn(0.52))O2. The material shows a discharge capacity of 292 mAh g(-1) at 0.2 C with capacity retention of 92% after 100 cycles. Moreover, a high discharge capacity of 78 mAh g(-1) could be obtained at 25 C. The exothermic temperature of the fully charged electrode is elevated from 203 to 261 °C with 50% reduction of the total thermal release, highlighting excellent thermal safety of the material.

  11. Faraday efficiency and mechanism of electrochemical surface reactions: CO2 reduction and H2 formation on Pt(111).

    PubMed

    Hussain, Javed; Jónsson, Hannes; Skúlason, Egill

    2016-12-22

    An atomic scale model of the electrical double layer is used to calculate the mechanism and rate of electrochemical reduction of CO2 as well as H2 formation at a Pt(111) electrode. The water layer contains solvated protons and the electrode has excess electrons at the surface. Density functional theory within the generalized gradient approximation is used to describe the electronic structure while the mechanism and activation energy of the various elementary reactions is obtained by calculating minimum energy paths using the nudged elastic band method. The applied electrical potential is deduced from the calculated work function. The optimal reaction mechanism for CO2 reduction to either methane or methanol is found and the estimated rate compared with that of the competing reaction, H2 formation. When the free energy of only the intermediates and reactants is taken into account, not the activation energy, Pt(111) would seem to be a good electrocatalyst for CO2 reduction, significantly better than Cu(111). This, however, contradicts experimental findings. Detailed calculations reported here show that the activation energy for CO2 reduction is high for both Heyrovsky and Tafel mechanisms on Pt(111) in the relevant range of applied potential. The rate-limiting step of the Heyrovsky mechanism, *COOH + H(+) + e(-) → *CO + H2O, is estimated to have an activation energy of 0.95 eV at -0.9 V vs. standard hydrogen electrode. Under the same conditions, the activation energy for H2 formation is estimated to be only 0.5 eV. This explains why attempts to reduce CO2 using platinum electrodes have produced only H2. A comparison is made with analogous results for Cu(111) [J. Hussain et al., Procedia Comput. Sci., 2015, 51, 1865] where a reaction mechanism with low activation energy for CO2 electroreduction to methane was identified. The difference between the two electrocatalysts is discussed.

  12. Not just fractal surfaces, but surface fractal aggregates: Derivation of the expression for the structure factor and its applications

    NASA Astrophysics Data System (ADS)

    Besselink, R.; Stawski, T. M.; Van Driessche, A. E. S.; Benning, L. G.

    2016-12-01

    Densely packed surface fractal aggregates form in systems with high local volume fractions of particles with very short diffusion lengths, which effectively means that particles have little space to move. However, there are no prior mathematical models, which would describe scattering from such surface fractal aggregates and which would allow the subdivision between inter- and intraparticle interferences of such aggregates. Here, we show that by including a form factor function of the primary particles building the aggregate, a finite size of the surface fractal interfacial sub-surfaces can be derived from a structure factor term. This formalism allows us to define both a finite specific surface area for fractal aggregates and the fraction of particle interfacial sub-surfaces at the perimeter of an aggregate. The derived surface fractal model is validated by comparing it with an ab initio approach that involves the generation of a "brick-in-a-wall" von Koch type contour fractals. Moreover, we show that this approach explains observed scattering intensities from in situ experiments that followed gypsum (CaSO4 ṡ 2H2O) precipitation from highly supersaturated solutions. Our model of densely packed "brick-in-a-wall" surface fractal aggregates may well be the key precursor step in the formation of several types of mosaic- and meso-crystals.

  13. Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2

    SciTech Connect

    Hod, Idan; Sampson, Matthew D.; Deria, Pravas; Kubiak, Clifford P.; Farha, Omar K.; Hupp, Joseph T.

    2015-09-18

    Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (~1015 sites/cm2). The chemical products of the reduction, obtained with ~100% Faradaic efficiency, are mixtures of CO and H2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.

  14. A chemical, morphological, and electrochemical (XPS, SEM/EDX, CV, and EIS) analysis of electrochemically modified electrode surfaces of natural chalcopyrite (CuFeS2) and pyrite (FeS2) in alkaline solutions.

    PubMed

    Velásquez, Pablo; Leinen, Dietmar; Pascual, José; Ramos-Barrado, José Ramón; Grez, Paula; Gómez, Humberto; Schrebler, Ricardo; Del Río, Rodrigo; Córdova, Ricardo

    2005-03-24

    Electrodic surfaces of natural chalcopyrite and natural pyrite minerals (El Teniente mine, Chile) have been studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy including microanalysis (SEM/EDX). For comparison, fractured and polished mineral surfaces were also studied by XPS. In both electrodes, the formation of Fe(III) species containing oxygen were detected and Cu(II) species containing oxygen were additionally detected for chalcopyrite at advanced oxidation states. The presence of Cu(II) species containing oxygen was not detected by XPS for the initial oxidation states of the chalcopyrite. For pyrite, the present results do not allow confirmation of the presence of polysulfurs such as have been previously proposed. In both minerals, the measurements of SEM and EDX show relevant alterations in the respective surfaces when different potential values were applied. The chalcopyrite surface shows the formation of protrusions with a high concentration of oxygen. The pyrite surface shows a layer of modified material with high oxygen content. The modifications detected by XPS, SEM, and EDX allowed the explanation of the complexity of the equivalent circuit used to simulate the experimental EIS data. At high oxidation states, both minerals showed a pseudoinductive loop in the equivalent circuit, which was due to the active electrodissolution of the minerals which takes place through a surface film previously formed.

  15. Detection of Single-Nucleotide Polymorphism on uidA Gene of Escherichia coli by a Multiplexed Electrochemical DNA Biosensor with Oligonucleotide-Incorporated Nonfouling Surface

    PubMed Central

    Liu, Gang; Lao, Ruojun; Xu, Li; Xu, Qin; Li, Lanying; Zhang, Min; Shen, Hao; Mathur, Sanjay; Fan, Chunhai; Song, Shiping

    2011-01-01

    We report here a practical application of a multiplexed electrochemical DNA sensor for highly specific single-nucleotide polymorphism (SNP) detection. In this work, a 16-electrode array was applied with an oligonucleotide-incorporated nonfouling surfaces (ONS) on each electrode for the resistance of unspecific absorption. The fully matched target DNA templated the ligation between the capture probe assembled on gold electrodes and the tandem signal probe with a biotin moiety, which could be transduced to peroxidase-based catalyzed amperometric signals. A mutant site (T93G) in uidA gene of E. coli was analyzed in PCR amplicons. 10% percentage of single mismatched mutant gene was detected, which clearly proved the selectivity of the multiplexed electrochemical DNA biosensor when practically applied. PMID:22164059

  16. Electrochemically mediated atom transfer radical polymerization from a substrate surface manipulated by bipolar electrolysis: fabrication of gradient and patterned polymer brushes.

    PubMed

    Shida, Naoki; Koizumi, Yuki; Nishiyama, Hiroki; Tomita, Ikuyoshi; Inagi, Shinsuke

    2015-03-23

    We report the first ever use of electrochemically mediated atom transfer radical polymerization (eATRP) employing a bipolar electrochemical method for the fabrication of both gradient and patterned polymer brushes. A potential gradient generated on a bipolar electrode allowed the formation of a concentration gradient of a Cu(I) polymerization catalyst through the one-electron reduction of Cu(II) , resulting in the gradient growth of poly(NIPAM) brushes from an initiator-modified substrate surface set close to a bipolar electrode. These polymer brushes could be fabricated in three-dimensional gradient shapes with control over thickness, steepness, and modified area by varying the electrolytic conditions. Moreover, by site-selective application of potential during bipolar electrolysis, a polymer brush with a circular pattern was successfully formed. Polymerization was achieved using both a polar monomer (NIPAM) and a nonpolar monomer (MMA) with the eATRP system.

  17. LiMPO4 and derived NaMPO4 (M = Mn, Fe, Mg) with excellent electrochemical properties for lithium/sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Zou, Bang-Kun; Shao, Yu; Qiang, Zi-Yue; Liao, Jia-Ying; Tang, Zhong-Feng; Chen, Chun-Hua

    2016-12-01

    A simple two-step solid-state-reaction process is adopted to synthesize carbon-coated Mg-doped Li(Mn,Fe)PO4 (LMMFP) nano-particles. As positive electrode materials for lithium-ion batteries, the carbon-coated LMMFP samples show excellent electrochemical properties in a temperature range from -20 to 55 °C. For example, LiMn0.48Fe0.5Mg0.02PO4 can deliver a capacity of 146.2 mAh g-1 at 3C rate and retain 95.3% after 450 cycles at 25 °C. It can also deliver 160.7 mAh g-1 at 1C and retain 97.7% after 100 cycles at 55 °C. Even at -20 °C, it gives a capacity of 109.5 mAh g-1 with an average discharge voltage of 3.37 V at 0.2C. In Na/LMMFP cells, the LMMFP electrodes can be electrochemically converted into Mg-doped Na(Mn,Fe)PO4 (NMMFP) electrodes for sodium-ion batteries (SIBs). Ex-situ XRD proves that the derived NMMFP have an olivine-type structure and can reversibly extract and insert sodium ions. For example, NaMn0.48Fe0.5Mg0.02PO4 can deliver a reversible specific capacity of 126.9 mAh g-1 after 30 cycles at 0.1C with an average discharge voltage of 3.1 V. This study opens up a new direction on exploring olivine-type SIB cathodes.

  18. Electrochemical Atomic Layer Processing

    DTIC Science & Technology

    1994-06-25

    where an atomic layer of an element is deposited , or removed, in a surface limited reaction. The potentials used are referred to as underpotentials in...the electrochemical literature. The atomic layer deposition process is referred to as underpotential deposition (UPD). 14. SUBJECT TERMS 15, NUMBER OF...reaction. The potentials used are referred to as underpotentials in the electrochemical literature. The atomic layer deposition process is referred to as

  19. Kinetics of electrochemically controlled surface reactions on bulk and thin film metals studied with Fourier transform impedance spectroscopy and surface plasmon resonance techniques

    NASA Astrophysics Data System (ADS)

    Assiongbon, Kankoe A.

    2005-07-01

    In the work presented in this thesis, the surface sensitive electrochemical techniques of cyclic voltametry (CV), potential step (PS) and Fourier transform impedance spectroscopy (FT-EIS), as well as the optical technique of surface plasmon resonance (SPR), were used to probe a wide variety of surface processes at various metal/liquid interface. Three polycrystalline metals (Au, Ta and Cu) and a Cr-coated gold film were used for these studies in different aqueous environments. A combination of CV with FT-EIS and PS was used to investigate electronic and structural proprieties of a modified bulk electrode of Au. This experimental system involved under potential deposition (UPD) of Bi3+ on Au in a supporting aqueous electrolyte containing ClO-4 . UPD range of Bi3+ was determined, and adsorption kinetics of Bi3+ in the presence of coadsorbing anion, ClO-4 were quantified. Potentiodynamic growth of oxide films of Ta in the following electrolytes NaNO3, NaNO3 + 5wt% H2O2, NaOH and NaOH + 5wt% H2O2 had been investigated. The oxide films were grown in the range -0.1 → +0.4V (high electric field) at a scan rate of 10 mV/s. Time resolved A.C. impedance spectroscopy measurements in the frequency range (0.1--20 KHz) were performed to characterize the surface reactions of oxide formation. The results are interpreted in terms of charge conductivity O2- through the oxide film, and disintegration of H2O2 into OH-. In a high pH medium (pH 12), dissociation of H2O2 was catalytically enhanced. This led to destabilization of the electrogenerated tantalum oxide surface film in the form of a soluble hexatantalate species. In contrast with the electrolytes, NaNO3, NaNO3 + 5wt% H2O2, NaOH, where only the oxide growth was observed, the A.C. impedance spectroscopy measurements in NaOH + 5wt% H 2O2 showed competition between oxide formation and its removal. These results are relevant for chemical slurry design in chemical mechanical polishing (CMP) of Ta. Further investigations were

  20. Wettability Control of Gold Surfaces Modified with Benzenethiol Derivatives: Water Contact Angle and Thermal Stability.

    PubMed

    Tatara, Shingo; Kuzumoto, Yasutaka; Kitamura, Masatoshi

    2016-04-01

    The water wettability of Au surfaces has been controlled using various benzenethiol derivatives including 4-methylbenzenethiol, pentafluorobenzenethiol, 4-flubrobenzenethiol, 4-methoxy-benzenethiol, 4-nitrobenzenethiol, and 4-hydroxybenzenethiol. The water contact angle of the Au surface modified with the benzenethiol derivative was found to vary in the wide range of 30.9° to 88.3°. The contact angle of the modified Au films annealed was also measured in order to investigate their thermal stability. The change in the contact angle indicated that the modified surface is stable at temperatures below about 400 K. Meanwhile, the activation energy of desorption from the modified surface was estimated from the change in the contact angle. The modified Au surface was also examined using X-ray photoelectron spectroscopy.

  1. Effect of surface modification by nitrogen ion implantation on the electrochemical and cellular behaviors of super-elastic NiTi shape memory alloy.

    PubMed

    Maleki-Ghaleh, H; Khalil-Allafi, J; Sadeghpour-Motlagh, M; Shakeri, M S; Masoudfar, S; Farrokhi, A; Beygi Khosrowshahi, Y; Nadernezhad, A; Siadati, M H; Javidi, M; Shakiba, M; Aghaie, E

    2014-12-01

    The aim of this investigation was to enhance the biological behavior of NiTi shape memory alloy while preserving its super-elastic behavior in order to facilitate its compatibility for application in human body. The surfaces of NiTi samples were bombarded by three different nitrogen doses. Small-angle X-ray diffraction was employed for evaluating the generated phases on the bombarded surfaces. The electrochemical behaviors of the bare and surface-modified NiTi samples were studied in simulated body fluid (SBF) using electrochemical impedance and potentio-dynamic polarization tests. Ni ion release during a 2-month period of service in the SBF environment was evaluated using atomic absorption spectrometry. The cellular behavior of nitrogen-modified samples was studied using fibroblast cells. Furthermore, the effect of surface modification on super-elasticity was investigated by tensile test. The results showed the improvement of both corrosion and biological behaviors of the modified NiTi samples. However, no significant change in the super-elasticity was observed. Samples modified at 1.4E18 ion cm(-2) showed the highest corrosion resistance and the lowest Ni ion release.

  2. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    NASA Astrophysics Data System (ADS)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  3. Carbon-Coated Co(3+)-Rich Cobalt Selenide Derived from ZIF-67 for Efficient Electrochemical Water Oxidation.

    PubMed

    Li, Siwen; Peng, Sijia; Huang, Linsong; Cui, Xiaoqi; Al-Enizi, Abdullah M; Zheng, Gengfeng

    2016-08-17

    Oxygen evolution reaction (OER) electrocatalysts are confronted with challenges such as sluggish kinetics, low conductivity, and instability, restricting the development of water splitting. In this study, we report an efficient Co(3+)-rich cobalt selenide (Co0.85Se) nanoparticles coated with carbon shell as OER electrocatalyst, which are derived from zeolitic imidazolate framework (ZIF-67) precursor. It is proposed that the organic ligands in the ZIF-67 can effectively enrich and stabilize the Co(3+) ions in the inorganic-organic frameworks and subsequent carbon-coated nanoparticles. In alkaline media, the catalyst exhibits excellent OER performances, which are attributed to its abundant active sites, high conductivity, and superior kinetics.

  4. Investigation of possibility of surface rupture derived from PFDHA and calculation of surface displacement based on dislocation

    NASA Astrophysics Data System (ADS)

    Inoue, N.; Kitada, N.; Irikura, K.

    2013-12-01

    A probability of surface rupture is important to configure the seismic source, such as area sources or fault models, for a seismic hazard evaluation. In Japan, Takemura (1998) estimated the probability based on the historical earthquake data. Kagawa et al. (2004) evaluated the probability based on a numerical simulation of surface displacements. The estimated probability indicates a sigmoid curve and increases between Mj (the local magnitude defined and calculated by Japan Meteorological Agency) =6.5 and Mj=7.0. The probability of surface rupture is also used in a probabilistic fault displacement analysis (PFDHA). The probability is determined from the collected earthquake catalog, which were classified into two categories: with surface rupture or without surface rupture. The logistic regression is performed for the classified earthquake data. Youngs et al. (2003), Ross and Moss (2011) and Petersen et al. (2011) indicate the logistic curves of the probability of surface rupture by normal, reverse and strike-slip faults, respectively. Takao et al. (2013) shows the logistic curve derived from only Japanese earthquake data. The Japanese probability curve shows the sharply increasing in narrow magnitude range by comparison with other curves. In this study, we estimated the probability of surface rupture applying the logistic analysis to the surface displacement derived from a surface displacement calculation. A source fault was defined in according to the procedure of Kagawa et al. (2004), which determined a seismic moment from a magnitude and estimated the area size of the asperity and the amount of slip. Strike slip and reverse faults were considered as source faults. We applied Wang et al. (2003) for calculations. The surface displacements with defined source faults were calculated by varying the depth of the fault. A threshold value as 5cm of surface displacement was used to evaluate whether a surface rupture reach or do not reach to the surface. We carried out the

  5. Using surface-enhanced Raman spectroscopy and electrochemically driven melting to discriminate Yersinia pestis from Y. pseudotuberculosis based on single nucleotide polymorphisms within unpurified polymerase chain reaction amplicons.

    PubMed

    Papadopoulou, Evanthia; Goodchild, Sarah A; Cleary, David W; Weller, Simon A; Gale, Nittaya; Stubberfield, Michael R; Brown, Tom; Bartlett, Philip N

    2015-02-03

    The development of sensors for the detection of pathogen-specific DNA, including relevant species/strain level discrimination, is critical in molecular diagnostics with major impacts in areas such as bioterrorism and food safety. Herein, we use electrochemically driven denaturation assays monitored by surface-enhanced Raman spectroscopy (SERS) to target single nucleotide polymorphisms (SNPs) that distinguish DNA amplicons generated from Yersinia pestis, the causative agent of plague, from the closely related species Y. pseudotuberculosis. Two assays targeting SNPs within the groEL and metH genes of these two species have been successfully designed. Polymerase chain reaction (PCR) was used to produce Texas Red labeled single-stranded DNA (ssDNA) amplicons of 262 and 251 bases for the groEL and metH targets, respectively. These amplicons were used in an unpurified form to hybridize to immobilized probes then subjected to electrochemically driven melting. In all cases electrochemically driven melting was able to discriminate between fully homologous DNA and that containing SNPs. The metH assay was particularly challenging due to the presence of only a single base mismatch in the middle of the 251 base long PCR amplicon. However, manipulation of assay conditions (conducting the electrochemical experiments at 10 °C) resulted in greater discrimination between the complementary and mismatched DNA. Replicate data were collected and analyzed for each duplex on different days, using different batches of PCR product and different sphere segment void (SSV) substrates. Despite the variability introduced by these differences, the assays are shown to be reliable and robust providing a new platform for strain discrimination using unpurified PCR samples.

  6. Global detailed gravimetric geoid. [based on gravity model derived from satellite tracking and surface gravity data

    NASA Technical Reports Server (NTRS)

    Vincent, S.; Marsh, J. G.

    1973-01-01

    A global detailed gravimetric geoid has been computed by combining the Goddard Space Flight Center GEM-4 gravity model derived from satellite and surface gravity data and surface 1 deg-by-1 deg mean free air gravity anomaly data. The accuracy of the geoid is + or - 2 meters on continents, 5 to 7 meters in areas where surface gravity data are sparse, and 10 to 15 meters in areas where no surface gravity data are available. Comparisons have been made with the astrogeodetic data provided by Rice (United States), Bomford (Europe), and Mather (Australia). Comparisons have also been carried out with geoid heights derived from satellite solutions for geocentric station coordinates in North America, the Caribbean, Europe, and Australia.

  7. Asymmetric 1,3,4-oxadiazole derivatives containing naphthalene and stilbene units: synthesis, optical and electrochemical properties.

    PubMed

    Lu, Huixiong; He, Daohang

    2014-04-24

    Six novel asymmetric 1,3,4-oxadiazole derivatives containing naphthalene and stilbene units have been efficiently synthesized and characterized by FT-IR, (1)H NMR, (13)C NMR, mass spectrometry and elemental analysis. The UV-vis absorption maximum wavelength, fluorescence excitation wavelength, fluorescence emission wavelength and fluorescence quantum yield were measured in dilute tetrahydrofuran solution. The solvent effect was also studied. The HOMO and LUMO levels of these compounds were calculated by density functional theory (DFT) (B3LYP, 6-31G(*)) method and cyclic voltammetry. They emit bright violet to blue emission with high fluorescence quantum yields (0.23-0.94) and large Stokes shifts (53-102 nm). These compounds possess high HOMO levels (-5.03 to -5.17 eV) and suitable band gaps, indicating that they could be benefit for hole injection. The results show that they have a potential for application in optoelectronic materials.

  8. Can we derive ice flow from surface mass balance and surface elevation change?

    NASA Astrophysics Data System (ADS)

    Kuhn, M. H.; Olefs, M.

    2010-12-01

    Most likely we can not, or not exactly. The difference “delta” of surface mass balance and changes in surface elevation at one point or at one elevation band is the net result of two dimensional convergence of ice flow, advection of ice thickness by basal sliding, vertically integrated changes of firn density including creation and closing of voids in the ice, and basal melting. Here we present a series of delta values for 100 m elevation bands of Hintereisferner of the years 1953, 68, 79, 97, 2006. We believe that surface mass balance b and flow divergence du/dx dominate delta values in the accumulation area where surface elevation stayed constant within 10 m and we present evidence that basal melting has become important under the tongue since 1979. This is in accordance with a simultaneous, exponential decay of ice flow by one order of magnitude for Hintereisferner and other glaciers in the Alps. Based on observed delta values and measured ice thickness we attempt an extrapolation of thickness and area changes into coming years and calculate the associated melt water production for glaciers of various sizes.

  9. Synthesis of a novel hydrazone derivative and biophysical studies of its interactions with bovine serum albumin by spectroscopic, electrochemical, and molecular docking methods.

    PubMed

    Tian, Fang-Fang; Jiang, Feng-Lei; Han, Xiao-Le; Xiang, Chen; Ge, Yu-Shu; Li, Jia-Han; Zhang, Yue; Li, Ran; Ding, Xin-Liang; Liu, Yi

    2010-11-25

    Hydrazone derivatives possess potential antitumor activities based on modulation of the iron metabolism in cancer cell. A novel hydrazone, N'-(2,4-dimethoxybenzylidene)-2-hydroxybenzohydrazide (DBH), has been synthesized and characterized, which is an analogue of 311 possessing potent anticancer activity. The interactions between DBH and bovine serum albumin (BSA) have been investigated systematically by fluorescence, molecular docking, circular dichroism (CD), UV-vis absorption, and electrochemical impedance spectroscopy (EIS) methods under physiological conditions. The fluorescence quenching observed is attributed to the formation of a complex between BSA and DBH, and the reverse temperature effect of the fluorescence quenching has been found and discussed. The primary binding pattern is determined by hydrophobic interaction occurring in Sudlow's site I of BSA. DBH could slightly change the secondary structure and induce unfolding of the polypeptides of protein. An average binding distance of ~4.0 nm has been determined on the basis of the Förster resonance energy theory (FRET). The effects of iron on the system of DBH-BSA have also been investigated. It is found that iron could compete against BSA to bind DBH. All of these results are supported by a docking study using a BSA crystal model. It is shown that DBH can efficiently bind with BSA and be transported to the focuses needed. Subsequent antitumor test and detailed anticancer mechanism are undergoing in our lab.

  10. Evidence for the intrinsic nature of band-gap states electrochemically observed on atomically flat TiO2(110) surfaces.

    PubMed

    Takata, Shintaro; Miura, Yoshihiro; Matsumoto, Yuji

    2014-12-07

    Using an ultra-high vacuum (UHV) electrochemistry approach with pulsed laser deposition (PLD), we investigated the band-gap state for TiO2(110). In the PLD chamber, a TiO2(110) surface was cleaned by annealing in O2 enough for it to exhibit a sharp (1 × 1) reflection high energy electron diffraction (RHEED) pattern. The cleaned TiO2(110)-(1 × 1) sample then underwent electrochemical measurements without exposure to air, showing the band-gap state at -0.14 V vs. Ag by Mott-Schottky plot analysis. The band-gap state gradually disappeared under UV illumination at +0.6 V vs. Ag due to photoetching, and reappeared on reduction in a vacuum and/or deposition of a fresh TiO2 film. These results indicated that the electrochemically observed band-gap state for TiO2(110) was a defect state due to oxygen deficiency, most probably identical to that observed under UHV, which does not necessarily exist on the surface. A quantitative analysis of the defect density suggests that the origin of this defect state is not the surface bridging hydroxyls or oxygen vacancies, but rather the interstitial Ti(3+) ions in the subsurface region.

  11. Deriving the surface composition from particle measurements in orbit around Mercury

    NASA Astrophysics Data System (ADS)

    Wurz, P.; Rohner, U.; Whitby, J.; Lammer, H.; Massetti, S.; Orsini, S.

    We combine our three recent theoretical models (exopsheric density profiles, particle precipitation, and sputtering of minerals) to directly connect neutral particle densities measured in the exosphere with their respective surface densities. In addition, by reasonably constraining the number of minerals on Mercury's surface we can derive a mineralogical composition from the measured exospheric densities. The potential of this approach will be demonstrated using the existing data for the exospheric densities of H, O, Na, K, and Ca.

  12. Nitrogen-doped porous carbon derived from metal-organic gel for electrochemical analysis of heavy-metal ion.

    PubMed

    Cui, Lin; Wu, Jie; Ju, Huangxian

    2014-09-24

    A nitrogen-doped porous carbon material (N@MOG-C) was prepared by simple pyrolysis of polypyrrole-doped Al-based metal-organic gel (PPy@MOG) at 800 °C. The N@MOG-C possessed a uniform three-dimensional (3-D) interconnected mesoporous structure with a high surface area of 1542.6 m(2) g(-1) and a large pore volume of 0.76 cm(3) g(-1). By using an ionic liquid (IL) to immobilize N@MOG-C on electrode surface, the N@MOG-C was further used for sensitive detection of heavy metal ion. The doping of nitrogen-endowed N@MOG-C with faster electron transfer kinetics than other carbon materials such as MOG-C, multiwalled carbon nanotubes, and graphene. The N@MOG-C-modified electrode showed a high effective area, because of the porous structure. Under optimized conditions, the N@MOG-C-based sensor could detect Cd ions present in concentrations of 0.025-5 μM, with a detection limit of 2.2 nM. The mesoporous structure, fast electron transfer ability, and simple and green synthesis of N@MOG-C made it a promising electrode material for practical applications in heavy-metal-ion sensing.

  13. Hydroxyethyl cellulose as efficient organic inhibitor of zinc-carbon battery corrosion in ammonium chloride solution: Electrochemical and surface morphology studies

    NASA Astrophysics Data System (ADS)

    Deyab, M. A.

    2015-04-01

    Hydroxyethyl cellulose (HEC) has been investigated as corrosion inhibitor for zinc-carbon battery by polarization and electrochemical impedance spectroscopy (EIS) measurements. The obtained results show that the maximum inhibition efficiency by HEC in 26% NH4Cl solution at 300 ppm and 298 K is 92.07%. Tafel polarization studies reveal that HEC acts as an efficient mixed inhibitor. The corrosion rate is suppressed by the adsorption of HEC on the zinc surface. HEC adsorption obeys the Langmuir isotherm and the thermodynamic parameters Kads and Δ Gadso have been also calculated and discussed. Both physisorption and chemisorption may occur on the zinc surface. Surface characterization investigation using Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) is used to ascertain the nature of the protective film.

  14. Molecular association of 2-(n-alkylamino)-1,4-naphthoquinone derivatives: Electrochemical, DFT studies and antiproliferative activity against leukemia cell lines

    NASA Astrophysics Data System (ADS)

    Patil, Rishikesh; Bhand, Sujit; Konkimalla, V. Badireenath; Banerjee, Priyabrata; Ugale, Bharat; Chadar, Dattatray; Saha, Sourav Kr.; Praharaj, Prakash Priyadarshi; Nagaraja, C. M.; Chakrovarty, Debamitra; Salunke-Gawali, Sunita

    2016-12-01

    Molecular structures and their molecular association of 2-(n-alkylamino)-1,4-naphthoquinone, viz., LH-3; propyl, LH-4; butyl and LH-8; octyl derivatives were studied by single crystal X-ray diffraction studies. Synthesis and characterization of 2-octylamino-1,4-naphthoquinone; LH-8 was discussed. The molecule of LH-3 crystallizes in orthorhombic space group P21/c, while the LH-4 and LH-8 molecule crystallizes in triclinic space group P-1. LH-3, LH-4 and LH-8 showed intermolecular N-H⋯O and C-H⋯O interactions, LH-3 showed unique C(3)-H(3)⋯O(1) interaction. Interchain π-π stacking, slipped π-π stacking and C⋯O close contacts was respectively observed in LH-3, LH-4 and LH-8. Electrochemical studies were performed on first eight members of homologous series of 2-(n-alkylamino)-1,4-naphthoquinone (LH-1 to LH-8) by cyclic voltammetry. Naphthoquinone to naphthosemiquinone reversible redox couple was observed in all compounds ∼ E1/2 = -0.657 ± 0.05 V. HOMO-LUMO band gap was determined for the neutral form as well as the monoanionic radical form viz. naphthosemiquinone form of selected derivatives by DFT studies. It has been observed that the electron density is delocalized in the naphthoquinone ring in both neutral as well as one electron reduced form of compounds. Antiproliferative activity of LH-1 to LH-8 was evaluated against two cancer cell lines, THP1(acute monocytic leukemia) and K562(human immortalized myelogenous leukemia cell line) cells. It was observed that, in THP1 cells, compounds LH-2 and LH-3 are very active while LH-1, LH-4 and LH-6 were moderately active and LH-5, LH-7 and LH-8 were totally inactive. Contrastingly, in K562 cells all of the compounds were moderately active.

  15. Effect of UV and electrochemical surface treatments on the adsorption and reaction of linear alcohols on non-porous carbon fibre

    NASA Astrophysics Data System (ADS)

    Osbeck, S.; Ward, S.; Idriss, H.

    2013-04-01

    The adsorption properties of untreated, electrochemically treated and ultra-violet/ozone treated polyacrylonitrile based carbon fibres were investigated using temperature programmed desorption (TPD) on a series of linear alcohols as probes in order to understand its surface properties. Surface uptake was found to be sensitive to both the surface treatment and the nature of the adsorbates. Surface coverage increased with increasing alcohol chain due to the increase in their polarizability. It also increased with the level of surface oxygen of the fibres most likely because it facilitates the Osbnd H bond dissociation of the alcohol functional group. In addition, the desorption temperature (during TPD) tracked the surface oxygen levels (as determined from XPS O1s signal) suggesting increasing in the adsorption energy. The reactions of C1-C4 linear alcohols were also investigated on the surface of the fibre carbon. The main reaction was dehydrogenation to the corresponding aldehydes; the dehydration reaction to olefins was not observed. The dehydrogenation reaction was sensitive to the length of the alky chain. It was highest for methanol (to formaldehyde) and decreased with increasing the carbon number. Overall TPD of linear alcohols was shown to be a promising method for quantifying the level and strength of bonding occurring on carbon fibre surfaces.

  16. Influence of Surface Seawater and Atmospheric Conditions on the Ccn Activity of Ocean-Derived Aerosol

    NASA Astrophysics Data System (ADS)

    Quinn, P.; Bates, T. S.; Russell, L. M.; Frossard, A. A.; Keene, W. C.; Kieber, D. J.; Hakala, J. P.

    2012-12-01

    Ocean-derived aerosols are produced from direct injection into the atmosphere (primary production) and gas-to-particle conversion in the atmosphere (secondary production). These different production mechanisms result in a broad range of particle sizes that has implications for the impact of ocean-derived aerosol on climate. The chemical composition of ocean-derived aerosols is a result of a complex mixture of inorganic sea salt and organic matter including polysaccharides, proteins, amino acids, microorganisms and their fragments, and secondary oxidation products. Both production mechanisms and biological processes in the surface ocean impact the ability of ocean-derived aerosol to act as cloud condensation nuclei (CCN). In addition, CCN activity can be impacted by atmospheric processing that modifies particle size and composition after the aerosol is emitted from the ocean. To understand relationships between production mechanism, surface ocean biology, and atmospheric processing, measurements were made of surface ocean chlorophyll and dissolved organic matter; nascent sea spray aerosol freshly emitted from the ocean surface; and ambient marine aerosol. These measurements were made along the coast of California and in the North Atlantic between the northeast US and Bermuda. These regions include both eutrophic and oligotraphic waters and, thus, provide for observations over a wide range of ocean conditions.

  17. Comparison of QuikSCAT and GPS-Derived Ocean Surface Winds

    NASA Technical Reports Server (NTRS)

    Axelrad, Penina

    2001-01-01

    The Colorado Center for Astrodynamics has completed a study comparing ocean surface winds derived from GPS bistatic measurements with QuikSCAT wind fields. We have also compiled an extensive database of the bistatic GPS flight data collected by NASA Langley Research Center over the last several years. The GPS data are augmented with coincident data from QuikSCAT, buoys, TOPEX, and ERS.

  18. Heteroatom-enriched and renewable banana-stem-derived porous carbon for the electrochemical determination of nitrite in various water samples

    PubMed Central

    Madhu, Rajesh; Veeramani, Vediyappan; Chen, Shen-Ming

    2014-01-01

    For the first time, high-surface-area (approximately 1465 m2 g−1), highly porous and heteroatom-enriched activated carbon (HAC) was prepared from banana stems (Musa paradisiaca, Family: Musaceae) at different carbonization temperatures of 700, 800 and 900°C (HAC) using a simple and eco-friendly method. The amounts of carbon, hydrogen, nitrogen and sulfur in the HAC are 61.12, 2.567, 0.4315, and 0.349%, respectively. Using X-ray diffraction (XRD), CHNS elemental analysis, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, the prepared activated carbon appears amorphous and disordered in nature. Here, we used HAC for an electrochemical application of nitrite (NO2−) sensor to control the environmental pollution. In addition, HAC exhibits noteworthy performance for the highly sensitive determination of nitrite. The limit of detection (LODs) of the nitrite sensor at HAC-modified GCE is 0.07 μM. In addition, the proposed method was applied to determine nitrite in various water samples with acceptable results. PMID:24755990

  19. Fe(III)-based metal-organic framework-derived core-shell nanostructure: Sensitive electrochemical platform for high trace determination of heavy metal ions.

    PubMed

    Zhang, Zhihong; Ji, Hongfei; Song, Yingpan; Zhang, Shuai; Wang, Minghua; Jia, Changchang; Tian, Jia-Yue; He, Linghao; Zhang, Xiaojing; Liu, Chun-Sen

    2017-03-07

    A new core-shell nanostructured composite composed of Fe(III)-based metal-organic framework (Fe-MOF) and mesoporous Fe3O4@C nanocapsules (denoted as Fe-MOF@mFe3O4@mC) was synthesized and developed as a platform for determining trace heavy metal ions in aqueous solution. Herein, the mFe3O4@mC nanocapsules were prepared by calcining the hollow Fe3O4@C that was obtained using the SiO2 nanoparticles as the template, followed by composing the Fe-MOF. The Fe-MOF@mFe3O4@mC nanocomposite demonstrated excellent electrochemical activity, water stability and high specific surface area, consequently resulting in the strong biobinding with heavy-metal-ion-targeted aptamer strands. Furthermore, by combining the conformational transition interaction, which is caused by the formation of the G-quadruplex between a single-stranded aptamer and high adsorbed amounts of heavy metal ions, the developed aptasensor exhibited a good linear relationship with the logarithm of heavy metal ion (Pb(2+) and As(3+)) concentration over the broad range from 0.01 to 10.0nM. The detection limits were estimated to be 2.27 and 6.73 pM toward detecting Pb(2+) and As(3+), respectively. The proposed aptasensor showed good regenerability, excellent selectivity, and acceptable reproducibility, suggesting promising applications in environment monitoring and biomedical fields.

  20. Heteroatom-enriched and renewable banana-stem-derived porous carbon for the electrochemical determination of nitrite in various water samples.

    PubMed

    Madhu, Rajesh; Veeramani, Vediyappan; Chen, Shen-Ming

    2014-04-23

    For the first time, high-surface-area (approximately 1465 m(2) g(-1)), highly porous and heteroatom-enriched activated carbon (HAC) was prepared from banana stems (Musa paradisiaca, Family: Musaceae) at different carbonization temperatures of 700, 800 and 900 °C (HAC) using a simple and eco-friendly method. The amounts of carbon, hydrogen, nitrogen and sulfur in the HAC are 61.12, 2.567, 0.4315, and 0.349%, respectively. Using X-ray diffraction (XRD), CHNS elemental analysis, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, the prepared activated carbon appears amorphous and disordered in nature. Here, we used HAC for an electrochemical application of nitrite (NO2(-)) sensor to control the environmental pollution. In addition, HAC exhibits noteworthy performance for the highly sensitive determination of nitrite. The limit of detection (LODs) of the nitrite sensor at HAC-modified GCE is 0.07 μM. In addition, the proposed method was applied to determine nitrite in various water samples with acceptable results.

  1. Heteroatom-enriched and renewable banana-stem-derived porous carbon for the electrochemical determination of nitrite in various water samples

    NASA Astrophysics Data System (ADS)

    Madhu, Rajesh; Veeramani, Vediyappan; Chen, Shen-Ming

    2014-04-01

    For the first time, high-surface-area (approximately 1465 m2 g-1), highly porous and heteroatom-enriched activated carbon (HAC) was prepared from banana stems (Musa paradisiaca, Family: Musaceae) at different carbonization temperatures of 700, 800 and 900°C (HAC) using a simple and eco-friendly method. The amounts of carbon, hydrogen, nitrogen and sulfur in the HAC are 61.12, 2.567, 0.4315, and 0.349%, respectively. Using X-ray diffraction (XRD), CHNS elemental analysis, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, the prepared activated carbon appears amorphous and disordered in nature. Here, we used HAC for an electrochemical application of nitrite (NO2-) sensor to control the environmental pollution. In addition, HAC exhibits noteworthy performance for the highly sensitive determination of nitrite. The limit of detection (LODs) of the nitrite sensor at HAC-modified GCE is 0.07 μM. In addition, the proposed method was applied to determine nitrite in various water samples with acceptable results.

  2. Surface Glycoproteins of Exosomes Shed by Myeloid-Derived Suppressor Cells Contribute to Function.

    PubMed

    Chauhan, Sitara; Danielson, Steven; Clements, Virginia; Edwards, Nathan; Ostrand-Rosenberg, Suzanne; Fenselau, Catherine

    2017-01-06

    In this report, we use a proteomic strategy to identify glycoproteins on the surface of exosomes derived from myeloid-derived suppressor cells (MDSCs), and then test if selected glycoproteins contribute to exosome-mediated chemotaxis and migration of MDSCs. We report successful modification of a surface chemistry method for use with exosomes and identify 21 surface N-glycoproteins on exosomes released by mouse mammary carcinoma-induced MDSCs. These glycoprotein identities and functionalities are compared with 93 N-linked glycoproteins identified on the surface of the parental cells. As with the lysate proteomes examined previously, the exosome surface N-glycoproteins are primarily a subset of the glycoproteins on the surface of the suppressor cells that released them, with related functions and related potential as therapeutic targets. The "don't eat me" molecule CD47 and its binding partners thrombospondin-1 (TSP1) and signal regulatory protein α (SIRPα) were among the surface N-glycoproteins detected. Functional bioassays using antibodies to these three molecules demonstrated that CD47, TSP1, and to a lesser extent SIRPα facilitate exosome-mediated MDSC chemotaxis and migration.

  3. Aerosol optical depth under "clear" sky conditions derived from sea surface reflection of lidar signals.

    PubMed

    He, Min; Hu, Yongxiang; Huang, Jian Ping; Stamnes, Knut

    2016-12-26

    There are considerable demands for accurate atmospheric correction of satellite observations of the sea surface or subsurface signal. Surface and sub-surface reflection under "clear" atmospheric conditions can be used to study atmospheric correction for the simplest possible situation. Here "clear" sky means a cloud-free atmosphere with sufficiently small aerosol particles. The "clear" aerosol concept is defined according to the spectral dependence of the scattering cross section on particle size. A 5-year combined CALIPSO and AMSR-E data set was used to derive the aerosol optical depth (AOD) from the lidar signal reflected from the sea surface. Compared with the traditional lidar-retrieved AOD, which relies on lidar backscattering measurements and an assumed lidar ratio, the AOD retrieved through the surface reflectance method depends on both scattering and absorption because it is based on two-way attenuation of the lidar signal transmitted to and then reflected from the surface. The results show that the clear sky AOD derived from the surface signal agrees with the clear sky AOD available in the CALIPSO level 2 database in the westerly wind belt located in the southern hemisphere, but yields significantly higher aerosol loadings in the tropics and in the northern hemisphere.

  4. Intercomparison Between in situ and AVHRR Polar Pathfinder-Derived Surface Albedo over Greenland

    NASA Technical Reports Server (NTRS)

    Stroeve, Julienne C.; Box, Jason E.; Fowler, Charles; Haran, Terence; Key, Jeffery

    2001-01-01

    The Advanced Very High Resolution (AVHRR) Polar Pathfinder Data (APP) provides the first long time series of consistent, calibrated surface albedo and surface temperature data for the polar regions. Validations of these products have consisted of individual studies that analyzed algorithm performance for limited regions and or time periods. This paper reports on comparisons made between the APP-derived surface albedo and that measured at fourteen automatic weather stations (AWS) around the Greenland ice sheet from January 1997 to August 1998. Results show that satellite-derived surface albedo values are on average 10% less than those measured by the AWS stations. However, the station measurements tend to be biased high by about 4% and thus the differences in absolute albedo may be less (e.g. 6%). In regions of the ice sheet where the albedo variability is small, such as the dry snow facies, the APP albedo uncertainty exceeds the natural variability. Further work is needed to improve the absolute accuracy of the APP-derived surface albedo. Even so, the data provide temporally and spatially consistent estimates of the Greenland ice sheet albedo.

  5. How to Prevent the Loss of Surface Functionality Derived from Aminosilanes

    PubMed Central

    Asenath Smith, Emily; Chen, Wei

    2009-01-01

    Aminosilanes are common coupling agents used to functionalize silica surfaces. A major problem in applications of 3-aminopropylsilane-functionalized silica surfaces in aqueous media was encountered: the loss of covalently attached silane layers upon exposure to water at 40 °C. This is attributed to siloxane bond hydrolysis catalyzed by the amine functionality. To address the issue of loss of surface functionality and to find conditions where hydrolytically stable amine-functionalized surfaces can be prepared, silanization with different types of aminosilanes was carried out. Hydrolytic stability of the resulting silane-derived layers was examined as a function of reaction conditions and the structural features of the aminosilanes. Silane layers prepared in anhydrous toluene at elevated temperature are denser and exhibit greater hydrolytic stability than those prepared in the vapor phase at elevated temperature or in toluene at room temperature. Extensive loss of surface functionality was observed in all 3-aminopropylalkoxysilane-derived layers, independent of the number and the nature of the alkoxy groups. The hydrolytic stability of aminosilane monolayers derived from N-(6-aminohexyl)aminomethyltriethoxysilane (AHAMTES) indicates that the amine-catalyzed detachment can be minimized by controlling the length of the alkyl linker in aminosilanes. PMID:18834166

  6. Surface force measurements and simulations of mussel-derived peptide adhesives on wet organic surfaces.

    PubMed

    Levine, Zachary A; Rapp, Michael V; Wei, Wei; Mullen, Ryan Gotchy; Wu, Chun; Zerze, Gül H; Mittal, Jeetain; Waite, J Herbert; Israelachvili, Jacob N; Shea, Joan-Emma

    2016-04-19

    Translating sticky biological molecules-such as mussel foot proteins (MFPs)-into synthetic, cost-effective underwater adhesives with adjustable nano- and macroscale characteristics requires an intimate understanding of the glue's molecular interactions. To help facilitate the next generation of aqueous adhesives, we performed a combination of surface forces apparatus (SFA) measurements and replica-exchange molecular dynamics (REMD) simulations on a synthetic, easy to prepare, Dopa-containing peptide (MFP-3s peptide), which adheres to organic surfaces just as effectively as its wild-type protein analog. Experiments and simulations both show significant differences in peptide adsorption on CH3-terminated (hydrophobic) and OH-terminated (hydrophilic) self-assembled monolayers (SAMs), where adsorption is strongest on hydrophobic SAMs because of orientationally specific interactions with Dopa. Additional umbrella-sampling simulations yield free-energy profiles that quantitatively agree with SFA measurements and are used to extract the adhesive properties of individual amino acids within the context of MFP-3s peptide adhesion, revealing a delicate balance between van der Waals, hydrophobic, and electrostatic forces.

  7. Surface force measurements and simulations of mussel-derived peptide adhesives on wet organic surfaces

    PubMed Central

    Levine, Zachary A.; Rapp, Michael V.; Wei, Wei; Mullen, Ryan Gotchy; Wu, Chun; Zerze, Gül H.; Mittal, Jeetain; Waite, J. Herbert; Israelachvili, Jacob N.; Shea, Joan-Emma

    2016-01-01

    Translating sticky biological molecules—such as mussel foot proteins (MFPs)—into synthetic, cost-effective underwater adhesives with adjustable nano- and macroscale characteristics requires an intimate understanding of the glue’s molecular interactions. To help facilitate the next generation of aqueous adhesives, we performed a combination of surface forces apparatus (SFA) measurements and replica-exchange molecular dynamics (REMD) simulations on a synthetic, easy to prepare, Dopa-containing peptide (MFP-3s peptide), which adheres to organic surfaces just as effectively as its wild-type protein analog. Experiments and simulations both show significant differences in peptide adsorption on CH3-terminated (hydrophobic) and OH-terminated (hydrophilic) self-assembled monolayers (SAMs), where adsorption is strongest on hydrophobic SAMs because of orientationally specific interactions with Dopa. Additional umbrella-sampling simulations yield free-energy profiles that quantitatively agree with SFA measurements and are used to extract the adhesive properties of individual amino acids within the context of MFP-3s peptide adhesion, revealing a delicate balance between van der Waals, hydrophobic, and electrostatic forces. PMID:27036002

  8. Analytic height correlation function of rough surfaces derived from light scattering

    NASA Astrophysics Data System (ADS)

    Zamani, M.; Shafiei, F.; Fazeli, S. M.; Downer, M. C.; Jafari, G. R.

    2016-10-01

    We derive an analytic expression for the height correlation function of a homogeneous, isotropic rough surface based on the inverse wave scattering method of Kirchhoff theory. The expression directly relates the height correlation function to diffuse scattered intensity along a linear path at fixed polar angle. We test the solution by measuring the angular distribution of light scattered from rough silicon surfaces and comparing extracted height correlation functions to those derived from atomic force microscopy (AFM). The results agree closely with AFM over a wider range of roughness parameters than previous formulations of the inverse scattering problem, while relying less on large-angle scatter data. Our expression thus provides an accurate analytical equation for the height correlation function of a wide range of surfaces based on measurements using a simple, fast experimental procedure.

  9. Vacuum-vapor-deposited films based on benzo(a)phenoxazine derivatives under surface plasma fluorination

    NASA Astrophysics Data System (ADS)

    Agabekov, Vladimir E.; Ignasheva, Olga E.; Belyatsky, Vladimir N.

    1997-07-01

    Modification of vacuum vapor deposited thin films based on benzo(a)phenoxazone-5 derivatives with C3F8 and SF6 plasma were investigated. X-ray photoelectron spectroscopy (XPS) method was used to identify and study the distribution of surface functional groups of untreated and fluorinated films investigated. It was shown that fluor content in element composition of surface film layers and perfluorocarbon group content in Cls-lines of XP-spectra depended on chemical structure of the initial compounds. The more quantity and size of side substitutes were contained in the compound chemical structure the less was the content of fluor and perfluorocarbon groups in film surface fluorinated layer. The probable way of plasma active particle interaction with film surface is discussed. Using Kaelbe's method the influence of treatment conditions and initial compound chemical structure on surface properties of fluorinated films was studied.

  10. Hybrid Sol-Gel-Derived Films That Spontaneously Form Complex Surface Topographies.

    PubMed

    Destino, Joel F; Jones, Zachary R; Gatley, Caitlyn M; Zhang, Yi; Craft, Andrew K; Detty, Michael R; Bright, Frank V

    2016-10-04

    Surface patterns over multiple length scales are known to influence various biological processes. Here we report the synthesis and characterization of new, two-component xerogel thin films derived from carboxyethylsilanetriol (COE) and tetraethoxysilane (TEOS). Atomic force microscopy (AFM) reveals films surface with branched and hyper branched architectures that are ∼2 to 30 μm in diameter, that extend ∼3 to 1300 nm above the film base plane with surface densities that range from 2 to 77% surface area coverage. Colocalized AFM and Raman spectroscopy show that these branched structures are COE-rich domains, which are slightly stiffer (as shown from phase AFM imaging) and exhibit lower capacitive force in comparison with film base plane. Raman mapping reveals there are also discrete domains (≤300 nm in diameter) that are rich in COE dimers and densified TEOS, which do not appear to correspond with any surface structure seen by AFM.

  11. Electrochemical hydrogen storage of Ti-V-based body-centered-cubic phase alloy surface-modified with AB{sub 5} nanoparticles

    SciTech Connect

    Yu, X.B.; Walker, G.S.; Grant, D.M.; Wu, Z.; Xia, B.J.; Shen, J.

    2005-09-26

    A composite of Ti-V-based bcc phase alloy surface-modified with AB{sub 5} nanoparticles was prepared by ball milling. The composite showed significantly improved electrochemical hydrogen release capacities. For example, the 30 min ball milled Ti-30V-15Mn-15Cr+10 wt %AB{sub 5} showed a discharge capacity in the first cycle, at 353 K, of 886 mA h g{sup -1}, corresponding to 3.38 wt % of hydrogen, with a 45 mA g{sup -1} discharge current. It is thought that this high capacity is due to the enhanced electrochemical-catalytic activity from the alloy surface covered with AB{sub 5} nanoparticles, which not only have better charge-discharge capacity themselves, acting as both an electrocatalyst and a microcurrent collector, but also result in the greatly enhanced hydrogen atomic diffusivities in the nanocrystalline relative to their conventional coarse-grained counterparts. These results provide new insight for use of Ti-V-based bcc phase alloy for high-energy batteries.

  12. Electrochemical hydrogen storage of Ti-V-based body-centered-cubic phase alloy surface-modified with AB5 nanoparticles

    NASA Astrophysics Data System (ADS)

    Yu, X. B.; Walker, G. S.; Grant, D. M.; Wu, Z.; Xia, B. J.; Shen, J.

    2005-09-01

    A composite of Ti-V-based bcc phase alloy surface-modified with AB5 nanoparticles was prepared by ball milling. The composite showed significantly improved electrochemical hydrogen release capacities. For example, the 30 min ball milled Ti-30V-15Mn-15Cr +10wt%AB5 showed a discharge capacity in the first cycle, at 353 K, of 886mAhg-1, corresponding to 3.38 wt % of hydrogen, with a 45mAg-1 discharge current. It is thought that this high capacity is due to the enhanced electrochemical-catalytic activity from the alloy surface covered with AB5 nanoparticles, which not only have better charge-discharge capacity themselves, acting as both an electrocatalyst and a microcurrent collector, but also result in the greatly enhanced hydrogen atomic diffusivities in the nanocrystalline relative to their conventional coarse-grained counterparts. These results provide new insight for use of Ti-V-based bcc phase alloy for high-energy batteries.

  13. Preparation of nitrogen-doped cotton stalk microporous activated carbon fiber electrodes with different surface area from hexamethylenetetramine-modified cotton stalk for electrochemical degradation of methylene blue

    NASA Astrophysics Data System (ADS)

    Li, Kunquan; Rong, Zhang; Li, Ye; Li, Cheng; Zheng, Zheng

    Cotton-stalk activated carbon fibers (CSCFs) with controllable micropore area and nitrogen content were prepared as an efficient electrode from hexamethylenetetramine-modified cotton stalk by steam/ammonia activation. The influence of microporous area, nitrogen content, voltage and initial concentration on the electrical degradation efficiency of methylene blue (MB) was evaluated by using CSCFs as anode. Results showed that the CSCF electrodes exhibited excellent MB electrochemical degradation ability including decolorization and COD removal. Increasing micropore surface area and nitrogen content of CSCF anode leaded to a corresponding increase in MB removal. The prepared CSCF-800-15-N, which has highest N content but lowest microporous area, attained the best degradation effect with 97% MB decolorization ratio for 5 mg/L MB at 12 V in 4 h, implying the doped nitrogen played a prominent role in improving the electrochemical degradation ability. The electrical degradation reaction was well described by first-order kinetics model. Overall, the aforesaid findings suggested that the nitrogen-doped CSCFs were potential electrode materials, and their electrical degradation abilities could be effectively enhanced by controlling the nitrogen content and micropore surface area.

  14. Detection of Human IgG on Poly(pyrrole-3-carboxylic acid) Thin Film by Electrochemical-Surface Plasmon Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Janmanee, Rapiphun; Baba, Akira; Phanichphant, Sukon; Sriwichai, Saengrawee; Shinbo, Kazunari; Kato, Keizo; Kaneko, Futao

    2011-01-01

    An electrochemically controlled surface plasmon resonance (SPR) immunosensor for the detection of human immunoglobulin G (IgG) has been developed using poly(pyrrole-3-carboxylic acid) (PP3C) film. In this work, a pyrrole-3-carboxylic acid monomer was used for electropolymerization of a PP3C film on a gold-coated high-refractive-index glass slide. In situ electrochemical (EC)-SPR spectroscopy was performed to study the kinetic property and electroactivity property of the PP3C film. Moreover, ultraviolet-visible (UV-vis) spectroscopy was performed to characterize the PP3C film. Finally, the immunosensor-based PP3C film was constructed. The carboxylic acid surface of the PP3C film was activated for the immobilization of anti-human IgG. The immunosensor electrode was used for probing the binding reaction of anti-human IgG/human IgG with several concentrations of human IgG at different constant applied potentials. The probe immobilization and immunosensing process were in situ monitored by EC-SPR technique. The sensitivity of the sensor was improved by controlling the morphology of the PP3C film by applying the potential.

  15. Differences observed in the surface morphology and microstructure of Ni-Fe-Cu ternary thin films electrochemically deposited at low and high applied current densities

    NASA Astrophysics Data System (ADS)

    Sarac, U.; Kaya, M.; Baykul, M. C.

    2016-10-01

    In this research, nanocrystalline Ni-Fe-Cu ternary thin films using electrochemical deposition technique were produced at low and high applied current densities onto Indium Tin Oxide (ITO) coated conducting glass substrates. Change of surface morphology and microstructural properties of the films were investigated. Energy dispersive X-ray spectroscopy (EDX) measurements showed that the Ni-Fe-Cu ternary thin films exhibit anomalous codeposition behaviour during the electrochemical deposition process. From the X-ray diffraction (XRD) analyses, it was revealed that there are two segregated phases such as Cu- rich and Ni-rich within the films. The crystallographic structure of the films was face-centered cubic (FCC). It was also observed that the film has lower lattice micro-strain and higher texture degree at high applied current density. Scanning electron microscopy (SEM) studies revealed that the films have rounded shape particles on the base part and cauliflower-like structures on the upper part. The film electrodeposited at high current density had considerably smaller rounded shape particles and cauliflower-like structures. From the atomic force microscopy (AFM) analyses, it was shown that the film deposited at high current density has smaller particle size and surface roughness than the film grown at low current density.

  16. Derivation of Ground Surface and Vegetation in a Coastal Florida Wetland with Airborne Laser Technology

    USGS Publications Warehouse

    Raabe, Ellen A.; Harris, Melanie S.; Shrestha, Ramesh L.; Carter, William E.

    2008-01-01

    The geomorphology and vegetation of marsh-dominated coastal lowlands were mapped from airborne laser data points collected on the Gulf Coast of Florida near Cedar Key. Surface models were developed using low- and high-point filters to separate ground-surface and vegetation-canopy intercepts. In a non-automated process, the landscape was partitioned into functional landscape units to manage the modeling of key landscape features in discrete processing steps. The final digital ground surface-elevation model offers a faithful representation of topographic relief beneath canopies of tidal marsh and coastal forest. Bare-earth models approximate field-surveyed heights by + 0.17 m in the open marsh and + 0.22 m under thick marsh or forest canopy. The laser-derived digital surface models effectively delineate surface features of relatively inaccessible coastal habitats with a geographic coverage and vertical detail previously unavailable. Coastal topographic details include tidal-creek tributaries, levees, modest topographic undulations in the intertidal zone, karst features, silviculture, and relict sand dunes under coastal-forest canopy. A combination of laser-derived ground-surface and canopy-height models and intensity values provided additional mapping capabilities to differentiate between tidal-marsh zones and forest types such as mesic flatwood, hydric hammock, and oak scrub. Additional derived products include fine-scale shoreline and topographic profiles. The derived products demonstrate the capability to identify areas of concern to resource managers and unique components of the coastal system from laser altimetry. Because the very nature of a wetland system presents difficulties for access and data collection, airborne coverage from remote sensors has become an accepted alternative for monitoring wetland regions. Data acquisition with airborne laser represents a viable option for mapping coastal topography and for evaluating habitats and coastal change on marsh

  17. Fabrication of advanced electrochemical energy materials using sol-gel processing techniques

    NASA Technical Reports Server (NTRS)

    Chu, C. T.; Chu, Jay; Zheng, Haixing

    1995-01-01

    Advanced materials play an important role in electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. They are being used as both electrodes and electrolytes. Sol-gel processing is a versatile solution technique used in fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. The application of sol-gel processing in the fabrication of advanced electrochemical energy materials will be presented. The potentials of sol-gel derived materials for electrochemical energy applications will be discussed along with some examples of successful applications. Sol-gel derived metal oxide electrode materials such as V2O5 cathodes have been demonstrated in solid-slate thin film batteries; solid electrolytes materials such as beta-alumina for advanced secondary batteries had been prepared by the sol-gel technique long time ago; and high surface area transition metal compounds for capacitive energy storage applications can also be synthesized with this method.

  18. Electropolishing of stainless steels in a choline chloride based ionic liquid: an electrochemical study with surface characterisation using SEM and atomic force microscopy.

    PubMed

    Abbott, Andrew P; Capper, Glen; McKenzie, Katy J; Glidle, Andrew; Ryder, Karl S

    2006-09-28

    We have studied the anodic dissolution (electropolishing) of various stainless steel alloys in an ionic liquid comprising a 2 : 1 stoichiometric mix of ethylene glycol (EG) and choline chloride. We have used a combination of electrochemical and spectroscopic methods together with in situ liquid probe microscopy. We discuss the role and influence of the surface oxide passivation layer, characterized here by X-ray photoelectron spectroscopy (XPS) and linear sweep voltammetry, on the polishing process. We address the question of dealloying during the polish in order to contribute to our understanding of the viability of the ionic liquid as a replacement industrial electropolishing medium; the current commercial process uses a corrosive mixture of phosphoric and sulfuric acids. Also, we present data from ex situ and in situ liquid AFM studies giving both a qualitative and quantitative insight into the nature and scale of morphological changes at the steel surface during the polishing process.

  19. A Fast Method of Deriving the Kirchhoff Formula for Moving Surfaces

    NASA Technical Reports Server (NTRS)

    Farassat, F.; Posey, Joe W.

    2007-01-01

    The Kirchhoff formula for a moving surface is very useful in many wave propagation problems, particularly in the prediction of noise from rotating machinery. Several publications in the last two decades have presented derivations of the Kirchhoff formula for moving surfaces in both time and frequency domains. Here we present a method originally developed by Farassat and Myers in time domain that is both simple and direct. It is based on generalized function theory and the useful concept of imbedding the problem in the unbounded three-dimensional space. We derive an inhomogeneous wave equation with the source terms that involve Dirac delta functions with their supports on the moving data surface. This wave equation is then solved using the simple free space Green's function of the wave equation resulting in the Kirchhoff formula. The algebraic manipulations are minimal and simple. We do not need the Green's theorem in four dimensions and there is no ambiguity in the interpretation of any terms in the final formulas. Furthermore, this method also gives the simplest derivation of the classical Kirchhoff formula which has a fairly lengthy derivation in physics and applied mathematics books. The Farassat-Myers method can be used easily in frequency domain.

  20. Surface chemical functionalities affect the behavior of human adipose-derived stem cells in vitro

    NASA Astrophysics Data System (ADS)

    Liu, Xujie; Feng, Qingling; Bachhuka, Akash; Vasilev, Krasimir

    2013-04-01

    This study examines the effect of surface chemical functionalities on the behavior of human adipose-derived stem cells (hASCs) in vitro. Plasma polymerized films rich in amine (sbnd NH2), carboxyl (sbnd COOH) and methyl (sbnd CH3), were generated on hydroxyapatite (HAp) substrates. The surface chemical functionalities were characterized by X-ray photoelectron spectroscopy (XPS). The ability of different substrates to absorb proteins was evaluated. The results showed that substrates modified with hydrophilic functional group (sbnd COOH and sbnd NH2) can absorb more proteins than these modified with more hydrophobic functional group (sbnd CH3). The behavior of human adipose-derived stem cells (hASCs) cultured on different substrates was investigated in vitro: cell counting kit-8 (CCK-8) analysis was used to characterize cell proliferation, scanning electronic microscopy (SEM) analysis was used to characterize cell morphology and alkaline phosphatase (ALP) activity analysis was used to account for differentiation. The results of this study demonstrated that the sbnd NH2 modified surfaces encourage osteogenic differentiation; the sbnd COOH modified surfaces promote cell adhesion and spreading and the sbnd CH3 modified surfaces have the lowest ability to induce osteogenic differentiation. These findings confirmed that the surface chemical states of biomaterials can affect the behavior of hASCs in vitro.

  1. Nonlinear electrochemical relaxation around conductors.

    PubMed

    Chu, Kevin T; Bazant, Martin Z

    2006-07-01

    We analyze the simplest problem of electrochemical relaxation in more than one dimension-the response of an uncharged, ideally polarizable metallic sphere (or cylinder) in a symmetric, binary electrolyte to a uniform electric field. In order to go beyond the circuit approximation for thin double layers, our analysis is based on the Poisson-Nernst-Planck (PNP) equations of dilute solution theory. Unlike most previous studies, however, we focus on the nonlinear regime, where the applied voltage across the conductor is larger than the thermal voltage. In such strong electric fields, the classical model predicts that the double layer adsorbs enough ions to produce bulk concentration gradients and surface conduction. Our analysis begins with a general derivation of surface conservation laws in the thin double-layer limit, which provide effective boundary conditions on the quasineutral bulk. We solve the resulting nonlinear partial differential equations numerically for strong fields and also perform a time-dependent asymptotic analysis for weaker fields, where bulk diffusion and surface conduction arise as first-order corrections. We also derive various dimensionless parameters comparing surface to bulk transport processes, which generalize the Bikerman-Dukhin number. Our results have basic relevance for double-layer charging dynamics and nonlinear electrokinetics in the ubiquitous PNP approximation.

  2. Surface-Regulated Nano-SnO2/Pt3Co/C Cathode Catalysts for Polymer Electrolyte Fuel Cells Fabricated by a Selective Electrochemical Sn Deposition Method.

    PubMed

    Nagasawa, Kensaku; Takao, Shinobu; Nagamatsu, Shin-ichi; Samjeské, Gabor; Sekizawa, Oki; Kaneko, Takuma; Higashi, Kotaro; Yamamoto, Takashi; Uruga, Tomoya; Iwasawa, Yasuhiro

    2015-10-14

    We have achieved significant improvements for the oxygen reduction reaction activity and durability with new SnO2-nanoislands/Pt3Co/C catalysts in 0.1 M HClO4, which were regulated by a strategic fabrication using a new selective electrochemical Sn deposition method. The nano-SnO2/Pt3Co/C catalysts with Pt/Sn = 4/1, 9/1, 11/1, and 15/1 were characterized by STEM-EDS, XRD, XRF, XPS, in situ XAFS, and electrochemical measurements to have a Pt3Co core/Pt skeleton-skin structure decorated with SnO2 nanoislands at the compressive Pt surface with the defects and dislocations. The high performances of nano-SnO2/Pt3Co/C originate from efficient electronic modification of the Pt skin surface (site 1) by both the Co of the Pt3Co core and surface nano-SnO2 and more from the unique property of the periphery sites of the SnO2 nanoislands at the compressive Pt skeleton-skin surface (more active site 2), which were much more active than expected from the d-band center values. The white line peak intensity of the nano-SnO2/Pt3Co/C revealed no hysteresis in the potential up-down operations between 0.4 and 1.0 V versus RHE, unlike the cases of Pt/C and Pt3Co/C, resulting in the high ORR performance. Here we report development of a new class of cathode catalysts with two different active sites for next-generation polymer electrolyte fuel cells.

  3. Damping of short gravity-capillary waves due to oil derivatives film on the water surface

    NASA Astrophysics Data System (ADS)

    Sergievskaya, Irina; Ermakov, Stanislav; Lazareva, Tatyana

    2016-10-01

    In this paper new results of laboratory studies of damping of gravity-capillary waves on the water surface covered by kerosene are presented and compared with our previous analysis of characteristics of crude oil and diesel fuel films. Investigations of kerosene films were carried out in a wide range values of film thicknesses (from some hundreds millimetres to a few millimetres) and in a wide range of surface wave frequencies (from 10 to 27 Hz). The selected frequency range corresponds to the operating wavelengths of microwave, X- to Ka-band radars typically used for the ocean remote sensing. The studied range of film thickness covers typical thicknesses of routine spills in the ocean. It is obtained that characteristics of waves, measured in the presence of oil derivatives films differ from those for crude oil films, in particular, because the volume viscosity of oil derivatives and crude oil is strongly different. To retrieve parameters of kerosene films from the experimental data the surface wave damping was analyzed theoretically in the frame of a model of two-layer fluid. The films are assumed to be soluble, so the elasticity on the upper and lower boundaries is considered as a function of wave frequency. Physical parameters of oil derivative films were estimated when tuning the film parameters to fit theory and experiment. Comparison between wave damping due to crude oil, kerosene and diesel fuel films have shown some capabilities of distinguishing of oil films from remote sensing of short surface waves.

  4. Satellite-derived surface temperature and in situ measurement at Solfatara of Pozzuoli (Naples, Italy)

    NASA Astrophysics Data System (ADS)

    Silvestri, M.; Cardellini, C.; Chiodini, G.; Buongiorno, M. F.

    2016-06-01

    Ground thermal anomalies in volcanic-hydrothermal systems, where the outflow of hot fluids gives rise to fumarolic fields, soil degassing, and hot soils, have, up to now, rarely been investigated by using satellite. Here we report a comparison between surface temperature derived by satellite data and a large data set of measured soil temperatures and CO2 fluxes for a volcanic-hydrothermal system, the Solfatara of Pozzuoli (Campi Flegrei, Italy). Surface temperatures derived from ASTER (Advanced Spaceborne Thermal Emission and Reflection Radiometer) data are compared with soil temperatures and CO2 fluxes from four surveys performed in 2003, 2010, and in 2014. The good match between the spatial distributions of computed and measured temperatures suggests the adequacy of satellite data to describe the Solfatara thermal anomaly, while the correspondence between temperatures and CO2 fluxes, evidences the link between degassing and heating processes. The ASTER derived surface temperatures (14-37°C) are coherent with those measured in the soil (10-97°C at 10 cm depth), considering the effect of the thermal gradients which characterize the degassing area of Solfatara. This study shows that satellite data can be a very powerful tool with which to study surface thermal anomalies, and can provide a supplementary tool to monitor thermal evolution of restless volcanoes.

  5. A Note on Evaluation of Temporal Derivative of Hypersingular Integrals over Open Surface with Propagating Contour.

    PubMed

    Jaworski, Dawid; Linkov, Aleksandr; Rybarska-Rusinek, Liliana

    The short note concerns with elasticity problems involving singular and hypersingular integrals over open surfaces, specifically cracks, with the contour propagating in time. Noting that near a smooth part of a propagating contour the state is asymptotically plane, we focus on 1D hypersingular integrals and employ complex variables. By using the theory of complex variable singular and hypersingular integrals, we show that the rule for evaluation of the temporal derivative is the same as that for proper integrals. Being applied to crack problems the rule implies that the temporal derivative may be evaluated by differentiation under the integral sign.

  6. Electrochemical Activation Parameters for Surface-Attached Reactants Evaluation of Unimolecular Frequency Factors for Representative Ligand-Bridged Reactions.

    DTIC Science & Technology

    1983-04-01

    ferricinium- ferrocene couple in several solvents. Reaction entropies cannot be determined for the present redox couples on account of their chemical...M.J. Weaver, submitted for publication. (14) K.L. Guyer, S.W. Barr, M.J. Weaver in "Proc. Symp. on Electrocatalysis ", W.E. O’Grady, P.N. Ross, Jr...on Chemistry and Physics of Electrocatalysis ," J.D.E. McIntyre, M.J. Weaver, E. Yeager, Eds., Electrochemical Society, Pennington, N.J., in press. (16

  7. Effect of Different Titanium Surfaces on Maturation of Murine Bone Marrow-Derived Dendritic Cells

    PubMed Central

    Zheng, Xiaofei; Zhou, Fengjuan; Gu, Yifei; Duan, Xiaobo; Mo, Anchun

    2017-01-01

    Dendritic cells (DCs) play a pivotal role in the host response to implanted biomaterials. Osseointegration of titanium (Ti) implant is an immunological and inflammatory-driven process. However, the role of DCs in this complex process is largely unknown. This study aimed to investigate the effect of different Ti surfaces on DC maturation, and evaluate its subsequent potential on osteogenic differentiation of preosteoblasts. Murine bone marrow-derived DCs were seeded on Ti disks with different surface treatments, including pretreatment (PT), sandblasted/acid-etched (SLA) and modified SLA (modSLA) surface. Compared with DCs cultured on PT and SLA surfaces, the cells seeded on modSLA surface demonstrated a more round morphology with lower expression of CD86 and MHC-II, the DC maturation markers. Those cells also secreted high levels of anti-inflammatory cytokine IL-10 and TGF-β. Notably, addition of conditioned medium (CM) from modSLA-induced DCs significantly increased the mRNA expression of Runx2 and ALP as well as ALP activity by murine preosteoblast MC3T3-E1 cells. Our data demonstrated that Ti disks with different surfaces lead to differential DCs responses. PT and SLA surfaces induce DCs mature, while DCs seeded on modSLA-Ti surface maintain an immature phenotype and exhibit a potential of promoting osteogenic differentiation of MC3T3-E1 cells. PMID:28157196

  8. Effect of Different Titanium Surfaces on Maturation of Murine Bone Marrow-Derived Dendritic Cells

    NASA Astrophysics Data System (ADS)

    Zheng, Xiaofei; Zhou, Fengjuan; Gu, Yifei; Duan, Xiaobo; Mo, Anchun

    2017-02-01

    Dendritic cells (DCs) play a pivotal role in the host response to implanted biomaterials. Osseointegration of titanium (Ti) implant is an immunological and inflammatory-driven process. However, the role of DCs in this complex process is largely unknown. This study aimed to investigate the effect of different Ti surfaces on DC maturation, and evaluate its subsequent potential on osteogenic differentiation of preosteoblasts. Murine bone marrow-derived DCs were seeded on Ti disks with different surface treatments, including pretreatment (PT), sandblasted/acid-etched (SLA) and modified SLA (modSLA) surface. Compared with DCs cultured on PT and SLA surfaces, the cells seeded on modSLA surface demonstrated a more round morphology with lower expression of CD86 and MHC-II, the DC maturation markers. Those cells also secreted high levels of anti-inflammatory cytokine IL-10 and TGF-β. Notably, addition of conditioned medium (CM) from modSLA-induced DCs significantly increased the mRNA expression of Runx2 and ALP as well as ALP activity by murine preosteoblast MC3T3-E1 cells. Our data demonstrated that Ti disks with different surfaces lead to differential DCs responses. PT and SLA surfaces induce DCs mature, while DCs seeded on modSLA-Ti surface maintain an immature phenotype and exhibit a potential of promoting osteogenic differentiation of MC3T3-E1 cells.

  9. Electro-chemical grinding

    NASA Technical Reports Server (NTRS)

    Feagans, P. L.

    1972-01-01

    Electro-chemical grinding technique has rotation speed control, constant feed rates, and contour control. Hypersonic engine parts of nickel alloys can be almost 100% machined, keeping tool pressure at virtual zero. Technique eliminates galling and permits constant surface finish and burr-free interrupted cutting.

  10. Assessment of Provisional MODIS-derived Surfaces Related to the Global Carbon Cycle

    NASA Astrophysics Data System (ADS)

    Cohen, W. B.; Maiersperger, T. K.; Turner, D. P.; Gower, S. T.; Kennedy, R. E.; Running, S. W.

    2002-12-01

    The global carbon cycle is one of the most important foci of an emerging global biosphere monitoring system. A key component of such a system is the MODIS sensor, onboard the Terra satellite platform. Biosphere monitoring requires an integrated program of satellite observations, Earth-system models, and in situ data. Related to the carbon cycle, MODIS science teams routinely develop a variety of global surfaces such as land cover, leaf area index, and net primary production using MODIS data and functional algorithms. The quality of these surfaces must be evaluated to determine their effectiveness for global biosphere monitoring. A project called BigFoot (http://www.fsl.orst.edu/larse/bigfoot/) is an organized effort across nine biomes to assess the quality of the abovementioned surfaces: (1) Arctic tundra; (2) boreal evergreen needle-leaved forest; temperate (3) cropland, (4) grassland, (5) evergreen needle-leaved forest, and (6) deciduous broad-leaved forest; desert (7) grassland and (8) shrubland; and (9) tropical evergreen broad-leaved forest. Each biome is represented by a site that has an eddy-covariance flux tower that measures water vapor and CO2 fluxes. Flux tower footprints are relatively small-approximately 1 km2. BigFoot characterizes 25 km2 around each tower, using field data, Landsat ETM+ image data, and ecosystem process models. Our innovative field sampling design incorporates a nested spatial series to facilitate geostatistical analyses, samples the ecological variability at a site, and is logistically efficient. Field data are used both to develop site-specific algorithms for mapping/modeling the variables of interest and to characterize the errors in derived BigFoot surfaces. Direct comparisons of BigFoot- and MODIS-derived surfaces are made to help understand the sources of error in MODIS-derived surfaces and to facilitate improvements to MODIS algorithms. Results from four BigFoot sites will be presented.

  11. Labeling Cell Surface GPIs and GPI-Anchored Proteins through Metabolic Engineering with Artificial Inositol Derivatives.

    PubMed

    Lu, Lili; Gao, Jian; Guo, Zhongwu

    2015-08-10

    Glycosylphosphatidylinositol (GPI) anchoring of proteins to the cell surface is important for various biological processes, but GPI-anchored proteins are difficult to study. An effective strategy was developed for the metabolic engineering of cell-surface GPIs and GPI-anchored proteins by using inositol derivatives carrying an azido group. The azide-labeled GPIs and GPI-anchored proteins were then tagged with biotin on live cells through a click reaction, which allows further elaboration with streptavidin-conjugated dyes or other molecules. The strategy can be used to label GPI-anchored proteins with various tags for biological studies.

  12. Surface composition deviation of Cu2ZnSnS4 derivative powdered samples

    NASA Astrophysics Data System (ADS)

    Harel, S.; Guillot-Deudon, C.; Choubrac, L.; Hamon, J.; Lafond, A.

    2014-06-01

    Powdered samples of Cu2ZnSnS4 derivatives prepared through a solid-state route were investigated by both bulk (electron dispersive X-ray spectroscopy) and surface-sensitive (X-ray photoelectron spectroscopy) methods. We observe a deviation in composition between the surface and the bulk for all non-stoichiometric samples (both Cu-poor and Cu-rich). This behavior has already been observed for slightly Cu-poor CZTS thin films and is reminiscent of that of CIGSe compounds.

  13. Surfaces wettability and morphology modulation in a fluorene derivative self-assembly system

    NASA Astrophysics Data System (ADS)

    Cao, Xinhua; Gao, Aiping; Zhao, Na; Yuan, Fangyuan; Liu, Chenxi; Li, Ruru

    2016-04-01

    A new organogelator based on fluorene derivative (gelator 1) was designed and synthesized. Organogels could be obtained via the self-assembly of the derivative in acetone, toluene, ethyl acetate, hexane, DMSO and petroleum ether. The self-assembly process was thoroughly characterized using field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), UV-vis, FT-IR and the contact angle. Surfaces with different morphologies and wetting properties were formed via the self-assembly of gelator 1 in the six different solvents. Interestingly, a superhydrophobic surface with a contact angle of 150° was obtained from organogel 1 in DMSO and exhibited the lotus-effect. The sliding angle necessary for a water droplet to move on the glass was only 15°. Hydrogen bonding and van der Waals forces were attributed as the main driving forces for gel formation.

  14. Seasonal and nonseasonal variability of satellite-derived surface pigment concentration in the California Current

    NASA Technical Reports Server (NTRS)

    Strub, P. Ted; James, Corinne; Thomas, Andrew C.; Abbott, Mark R.

    1990-01-01

    The large-scale patterns of satellite-derived surface pigment concentration off the west coast of North America are presented and are averaged into monthly mean surface wind fields over the California Current system (CCS) for the July 1979 to June 1986 period. The patterns are discussed in terms of both seasonal and nonseasonal variability for the indicated time period. The large-scale seasonal characteristics of the California Current are summarized. The data and methods used are described, and the problems known to affect the satellite-derived pigment concentrations and the wind data used in the study are discussed. The statistical analysis results are then presented and discussed in light of past observations and theory. Details of the CZCS data processing are described, and details of the principal estimator pattern methodology used here are given.

  15. Electrochemical and vibrational spectroscopic studies of coadsorption: Formation of mixed monolayers of methylene blue and long-chain dithioethers at sulfur-modified polycrystalline gold surfaces

    SciTech Connect

    Barner, B.J.; Corn, R.M. )

    1990-05-01

    Molecular conformation and order within mixed monolayers of methylene blue, sulfide, and the long-chain dithioether C{sub 14}H{sub 29}SC{sub 2}H{sub 4}SC{sub 14}H{sub 29} adsorbed onto polycrystalline evaporated gold films are studied by using electrochemical methods and ex situ vibrational spectroscopy. The methylene blue dye molecules directly chemisorb onto the sulfur-modified gold surface and do not significantly partition into the alkyl portions of the monolayer. However, upon reduction to leucomethylene blue, the dye molecules do partition into the alkyl subphase. Repeated electrochemical reduction and oxidation of the chemisorbed methylene blue result in an ordering of the adsorbed alkyl chains from a liquid-like structure to a close-packed configuration. The presence of a partial dithioether monolayer also leads to the formation of a stabilized leucomethylene blue film. The variations of the molecular structure observed in these mixed systems arise from the competing processes of chemisorption, aggregation, and hydrophobic solubilization occurring within the thin film.

  16. Synthesis of water-compatible surface-imprinted polymer via click chemistry and RAFT precipitation polymerization for highly selective and sensitive electrochemical assay of fenitrothion.

    PubMed

    Zhao, Lijuan; Zhao, Faqiong; Zeng, Baizhao

    2014-12-15

    A novel water-compatible fenitrothion imprinted polymer was prepared on Au nanoparticles (AuNPs) by click chemistry and reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization (RAFTPP). The RAFT chain-transfer agent was synthesized on the surface of AuNPs using click chemistry, then an imprinted polymer with hydrophilic polymer brushes was prepared on the RAFT chain-transfer agent modified AuNPs by RAFTPP, mediated by hydrophilic polyethylene glycol macromolecular cochain-transfer agent. The obtained molecularly imprinted material showed improved accessibility to fenitrothion and recognition property in water medium. When the material was immobilized on an ionic liquid functionalized graphene coated glassy carbon electrode for the electrochemical determination of fenitrothion, the resulting electrochemical sensor presented linear response in the range of 0.01-5 μM, with a sensitivity of 6.1 μA/μM mm(2). The low limit of detection was 8 nM (S/N=3). The sensor was successfully applied to the determination of real samples and the recovery for standard added was 95-108%.

  17. Highly sensitive and surface-renewable electrochemical quartz crystal microbalance assays of heparin and chondroitin sulfate based on their effects on the electrodeposition of neutral red.

    PubMed

    Yu, Rongmin; Ma, Ming; Wang, Lingling; Xie, Qingji; Cao, Zhijun; Jiang, Xueqin; Yao, Shouzhuo

    2009-02-15

    The electrochemical quartz crystal microbalance (EQCM) technique was used to investigate the electrochemistry of neutral red (NR) in phosphate buffer solution (PBS) and the effects of coexisting heparin (Hep) or chondroitin sulfate (CS) for the first time. The pH dependence of the electrochemistry of NR was examined, and a V-shaped frequency response (versus time) was observed during the cyclic voltammetric experiment of NR in a nearly neutral medium (pH ca. 6.10-7.00), being due to the electrodeposition and stripping of the poorly soluble reduced product of NR (NR(Red)) at these pH values. The effects of potential scan rate, the concentration of NR, and several supporting electrolytes were examined at pH 6.80. The V-shaped response to the redox switching of NR was weakened by the introduction of Hep or CS, being due to the increased inhibition of the NR(Red) electrodeposition probably via the electrostatic interaction of the NR and especially the NR(Red) with Hep or CS. The height of the V-shaped response decreases with the increase of Hep or CS concentration, with limits of detection down to 3 nmol L(-1) for Hep and 2 nmol L(-1) for CS, respectively. The novel and surface-regenerable EQCM assay protocol based on the electrochemically switchable deposition of a dye is highly recommended for wide biosensing applications.

  18. Ultrasensitive electrochemical immunoassay for surface array protein, a Bacillus anthracis biomarker using Au-Pd nanocrystals loaded on boron-nitride nanosheets as catalytic labels.

    PubMed

    Sharma, Mukesh Kumar; Narayanan, J; Pardasani, Deepak; Srivastava, Divesh N; Upadhyay, Sanjay; Goel, Ajay Kumar

    2016-06-15

    Bacillus anthracis, the causative agent of anthrax, is a well known bioterrorism agent. The determination of surface array protein (Sap), a unique biomarker for B. anthracis can offer an opportunity for specific detection of B. anthracis in culture broth. In this study, we designed a new catalytic bionanolabel and fabricated a novel electrochemical immunosensor for ultrasensitive detection of B. anthracis Sap antigen. Bimetallic gold-palladium nanoparticles were in-situ grown on poly (diallyldimethylammonium chloride) functionalized boron nitride nanosheets (Au-Pd NPs@BNNSs) and conjugated with the mouse anti-B. anthracis Sap antibodies (Ab2); named Au-Pd NPs@BNNSs/Ab2. The resulting Au-Pd NPs@BNNSs/Ab2 bionanolabel demonstrated high catalytic activity towards reduction of 4-nitrophenol. The sensitivity of the electrochemical immunosensor along with redox cycling of 4-aminophenol to 4-quinoneimine was improved to a great extent. Under optimal conditions, the proposed immunosensor exhibited a wide working range from 5 pg/mL to 100 ng/mL with a minimum detection limit of 1 pg/mL B. anthracis Sap antigen. The practical applicability of the immunosensor was demonstrated by specific detection of Sap secreted by the B. anthracis in culture broth just after 1h of growth. These labels open a new direction for the ultrasensitive detection of different biological warfare agents and their markers in different matrices.

  19. Preparations, structures, and electrochemical studies of aryldiazene complexes of rhenium: syntheses of the first heterobinuclear and heterotrinuclear derivatives with bis(diazene) or bis(diazenido) bridging ligands.

    PubMed

    Albertin, G; Antoniutti, S; Bacchi, A; Ballico, G B; Bordignon, E; Pelizzi, G; Ranieri, M; Ugo, P

    2000-07-24

    ligand [Mn(CO)2(PPh2OEt)2(mu-4,4'-N2C6H4-C6H4N2)Fe(P(OEt)3)4]BPh4 (MnFe) was prepared by deprotonating the bis(aryldiazene) compound [Mn(CO)3(PPh2OEt)2(mu-4,4'-HN=NC6H4-C6H4N=NH)Fe(4- CH3C6H4CN)(P(OEt)3)4](BPh4)3. Finally, the binuclear compound [Re(CO)3(PPh2OEt)2(mu-4,4'-HN=NC6H4-C6H4N2)Fe(CO)2(P(OPh)3)2](BPh4)2 (ReFe) containing a diazene-diazenido bridging ligand was prepared by reacting [Re(CO)3(PPh2OEt)2(4,4'-HN=NC6H4-C6H4N identical to N)]+ with the FeH2(CO)2(P(OPh)3)2 hydride derivative. The electrochemical reduction of mono- and binuclear aryldiazene complexes of both rhenium (1-12) and the manganese, as well as heterobinuclear ReRu and MnRu complexes, was studied by means of cyclic voltammetry and digital simulation techniques. The electrochemical oxidation of the mono- and binuclear aryldiazenido compounds Mn(C6H5N2)(CO)2P2 and (Mn(CO)2P2)2(mu-4,4'-N2C6H4-C6H4N2) (P = PPh2OEt) was also examined. Electrochemical data show that, for binuclear compounds, the diazene bridging unit allows delocalization of electrons between the two different redox centers of the same molecule, whereas the two metal centers behave independently in the presence of the diazenido bridging unit.

  20. Electrochemical micro sensor

    DOEpatents

    Setter, Joseph R.; Maclay, G. Jordan

    1989-09-12

    A micro-amperometric electrochemical sensor for detecting the presence of a pre-determined species in a fluid material is disclosed. The sensor includes a smooth substrate having a thin coating of solid electrolytic material deposited thereon. The working and counter electrodes are deposited on the surface of the solid electrolytic material and adhere thereto. Electrical leads connect the working and counter electrodes to a potential source and an apparatus for measuring the change in an electrical signal caused by the electrochemical oxidation or reduction of the species. Alternatively, the sensor may be fabricated in a sandwich structure and also may be cylindrical, spherical or other shapes.

  1. Electrochemical Engineering

    ERIC Educational Resources Information Center

    Alkire, Richard

    1976-01-01

    Discusses an electrochemical engineering course that combines transport phenomena and basic physical chemistry. Lecture notes and homework problems are used instead of a textbook; an outline of lecture topics is presented. (MLH)

  2. Influence of alkyl chain length on the surface activity of antibacterial polymers derived from ROMP.

    PubMed

    Altay, Esra; Yapaöz, Melda Altıkatoğlu; Keskin, Bahadır; Yucesan, Gundoğ; Eren, Tarik

    2015-03-01

    The purpose of this study is to understand the antibacterial properties of cationic polymers on solid surfaces by investigating the structure-activity relationships. The polymer synthesis was carried via ring opening metathesis polymerization (ROMP) of oxanorbornene derivatives. Modulation of molecular weights and alkyl chain lengths of the polymers were studied to investigate the antibacterial properties on the glass surface. Fluorescein (Na salt) staining contact angle measurements were used to characterize the positive charge density and hydrophobicity on the polymer coated surfaces. Positive charge density for the surface coated polymers with molecular weights of 3000 and 10,000 g mol(-1) is observed to be in the range of 2.3-28.5 nmol cm(-2). The ROMP based cationic pyridinium polymer with hexyl unit exhibited the highest bactericidal efficiency against Escherichia coli on solid surface killing 99% of the bacteria in 5 min. However, phenyl and octyl functionalized quaternary pyridinium groups exhibited lower biocidal properties on the solid surfaces compared to their solution phase biocidal properties. Studying the effect of threshold polymer concentrations on the antibacterial properties indicated that changing the concentrations of polymer coatings on the solid surface dramatically influences antibacterial efficiency.

  3. Electrochemical Techniques

    SciTech Connect

    Chen, Gang; Lin, Yuehe

    2008-07-20

    Sensitive and selective detection techniques are of crucial importance for capillary electrophoresis (CE), microfluidic chips, and other microfluidic systems. Electrochemical detectors have attracted considerable interest for microfluidic systems with features that include high sensitivity, inherent miniaturization of both the detection and control instrumentation, low cost and power demands, and high compatibility with microfabrication technology. The commonly used electrochemical detectors can be classified into three general modes: conductimetry, potentiometry, and amperometry.

  4. A TECHNIQUE FOR ASSESSING THE ACCURACY OF SUB-PIXEL IMPERVIOUS SURFACE ESTIMATES DERIVED FROM LANDSAT TM IMAGERY

    EPA Science Inventory

    We developed a technique for assessing the accuracy of sub-pixel derived estimates of impervious surface extracted from LANDSAT TM imagery. We utilized spatially coincident
    sub-pixel derived impervious surface estimates, high-resolution planimetric GIS data, vector--to-
    r...

  5. The Impact of Surface Chemistry on Bio-derived Carbon Performance as Supercapacitor Electrodes

    NASA Astrophysics Data System (ADS)

    Alshareef, Niman H.; Whitehair, Daniel; Xia, Chuan

    2016-12-01

    In this study, we demonstrate that highly functionalized and porous carbons can be derived from palm-leaf waste using the template-free facile synthesis process. The derived carbons have high content of nitrogen dopant, high surface area, and various defects. Moreover, these carbons exhibit a high electrical conductivity (107 S m-1). Thanks to the high content of edge N (64.3%) and highly microporous nature (82% of microspores), these biomass-derived carbons show promising performance when used as supercapacitor electrodes. To be specific, these carbonaceous materials show a specific capacitance as high as 197 and 135 F g-1 at 2 and 20 A g-1 in three-electrode configuration, respectively. Furthermore, the symmetrical cells using palm-leaf-derived carbon show an energy density of 8.4 Wh Kg-1 at a power density of 0.64 kW Kg-1, with high cycling life stability (˜8% loss after 10,000 continuous charge-discharge cycles at 20 A g-1). Interestingly, as the power density increases from 4.4 kW kg-1 to 36.8 kW kg-1, the energy density drops slowly from 8.4 Wh kg-1 to 3.4 Wh kg-1. Getting such extremely high power density without significant loss of energy density indicates that these palm-leaf-derived carbons have excellent electrode performance as supercapacitor electrodes.

  6. The Impact of Surface Chemistry on Bio-derived Carbon Performance as Supercapacitor Electrodes

    NASA Astrophysics Data System (ADS)

    Alshareef, Niman H.; Whitehair, Daniel; Xia, Chuan

    2017-03-01

    In this study, we demonstrate that highly functionalized and porous carbons can be derived from palm-leaf waste using the template-free facile synthesis process. The derived carbons have high content of nitrogen dopant, high surface area, and various defects. Moreover, these carbons exhibit a high electrical conductivity (107 S m-1). Thanks to the high content of edge N (64.3%) and highly microporous nature (82% of microspores), these biomass-derived carbons show promising performance when used as supercapacitor electrodes. To be specific, these carbonaceous materials show a specific capacitance as high as 197 and 135 F g-1 at 2 and 20 A g-1 in three-electrode configuration, respectively. Furthermore, the symmetrical cells using palm-leaf-derived carbon show an energy density of 8.4 Wh Kg-1 at a power density of 0.64 kW Kg-1, with high cycling life stability (˜8% loss after 10,000 continuous charge-discharge cycles at 20 A g-1). Interestingly, as the power density increases from 4.4 kW kg-1 to 36.8 kW kg-1, the energy density drops slowly from 8.4 Wh kg-1 to 3.4 Wh kg-1. Getting such extremely high power density without significant loss of energy density indicates that these palm-leaf-derived carbons have excellent electrode performance as supercapacitor electrodes.

  7. Modification of the cellulosic component of hemp fibers using sulfonic acid derivatives: Surface and thermal characterization.

    PubMed

    George, Michael; Mussone, Paolo G; Bressler, David C

    2015-12-10

    The aim of this study was to characterize the surface, morphological, and thermal properties of hemp fibers treated with two commercially available, inexpensive, and water soluble sulfonic acid derivatives. Specifically, the cellulosic component of the fibers were targeted, because cellulose is not easily removed during chemical treatment. These acids have the potential to selectively transform the surfaces of natural fibers for composite applications. The proposed method proceeds in the absence of conventional organic solvents and high reaction temperatures. Surface chemical composition and signature were measured using gravimetric analysis, X-ray photoelectron spectroscopy (XPS) and Fourier transform infra-red spectroscopy (FTIR). XPS data from the treated hemp fibers were characterized by measuring the reduction in O/C ratio and an increase in abundance of the C-C-O signature. FTIR confirmed the reaction with the emergence of peaks characteristic of disubstituted benzene and amino groups. Grafting of the sulfonic derivatives resulted in lower surface polarity. Thermogravimetric analysis revealed that treated fibers were characterized by lower percent degradation between 200 and 300 °C, and a higher initial degradation temperature.

  8. Materials for electrochemical capacitors.

    PubMed

    Simon, Patrice; Gogotsi, Yury

    2008-11-01

    Electrochemical capacitors, also called supercapacitors, store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). They can complement or replace batteries in electrical energy storage and harvesting applications, when high power delivery or uptake is needed. A notable improvement in performance has been achieved through recent advances in understanding charge storage mechanisms and the development of advanced nanostructured materials. The discovery that ion desolvation occurs in pores smaller than the solvated ions has led to higher capacitance for electrochemical double layer capacitors using carbon electrodes with subnanometre pores, and opened the door to designing high-energy density devices using a variety of electrolytes. Combination of pseudo-capacitive nanomaterials, including oxides, nitrides and polymers, with the latest generation of nanostructured lithium electrodes has brought the energy density of electrochemical capacitors closer to that of batteries. The use of carbon nanotubes has further advanced micro-electrochemical capacitors, enabling flexible and adaptable devices to be made. Mathematical modelling and simulation will be the key to success in designing tomorrow's high-energy and high-power devices.

  9. Cytocompatibility of Wood-derived Cellulose Nanofibril Hydrogels with Different Surface Chemistry.

    PubMed

    Rashad, Ahmad; Mustafa, Kamal; Heggset, Ellinor Bœvre; Syverud, Kristin

    2017-03-06

    The current study aims to demonstrate the influence of the surface chemistry of wood-derived cellulose nanofibril (CNF) hydrogels on fibroblasts for tissue engineering applications. TEMPO-mediated oxidation or carboxymethylation pretreatments were employed to produce hydrogels with different surface chemistry. This study demonstrates, firstly, the gelation of CNF with cell culture medium and formation of stable hydrogels with improved rheological properties. Secondly, the response of mouse fibroblasts cultured on the surface of the hydrogels or sandwiched within the materials with respect to cytotoxicity, cell attachment, proliferation, morphology and migration. Indirect cytotoxicity tests showed no toxic effect of either hydrogel. The direct contact with the caroxymethylated hydrogel adversely influenced the morphology of the cells and limited their spreading, while typical morphology and spreading of cells was observed with the TEMPO-oxidized hydrogel. The porous fibrous structure may be a key to cell proliferation and migration in the hydrogels.

  10. Electrochemical functionalization of vertically aligned carbon nanotube arrays with molybdenum oxides for the development of a surface-charge-controlled sensor

    NASA Astrophysics Data System (ADS)

    Ye, Jian-Shan; Wen, Ying; Wei-DeZhang; Cui, Hui Fang; Xu, Guo Qin; Sheu, Fwu-Shan

    2006-08-01

    The modification of inorganic polymeric oxides at the surface of carbon nanotubes is of paramount importance for developing new sensors. In this study, molybdenum oxide (MoOx) film was electrodeposited on the surface of multi-walled carbon nanotubes (MWNTs) by cycling the potential between +0.20 and -0.80 V (versus 3 M KCl-Ag|AgCl) in Na2MoO4 solution. The MoOx-modified nanotube (MoOx/MWNT) electrode displays well-defined redox transitions in 5 mM H2SO4 or in phosphate buffer solution (PBS), which can be attributed to the reductive formation and the re-oxidation of hydrogen molybdenum oxides. X-ray photoelectron spectra (XPS) showed that the deposited MoOx films are mainly Mo6+ complexes. Both MWNT and MoOx/MWNT electrodes have ideal reversibility in 5 mM K3[Fe(CN)6] in 1 M KCl as supporting electrolytes at all sweep rates (0.02-1.00 V s-1) by cyclic voltammetry. The negatively charged surface of MoOx/MWNTs can further attract molecular cations such as Ru(NH3)63+. The MoOx/MWNT electrode exhibited electrocatalytic ability towards the reduction of bromate due to high surface area and the fast electron transfer rate of nanotubes. Thus, electrochemical modification of inorganic polymeric oxides on the carbon nanotube provides a simple method for the preparation of novel sensors.

  11. Effect of substrate surface treatment on electrochemically assisted photocatalytic activity of N-S co-doped TiO2 films

    NASA Astrophysics Data System (ADS)

    Parada-Gamboa, N. J.; Pedraza-Avella, J. A.; Meléndez, A. M.

    2017-01-01

    To investigate whether different metal surface treatments, performed on meshes of stainless steel 304 and titanium, affect the photocatalytic activity (PCA) of supported modified anodic TiO2 films, metallic substrates were coated with titanium isopropoxide sol-gel precursor modified with thiourea. Substrates were pretreated by some of the following techniques: a) sandblasting, b) pickling, c) hydroxylation and d) passivation. The as-prepared electrode materials were characterized by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and voltammetry in the dark and under light UVA irradiation. PCA of modified N-S-TiO2 electrodes was evaluated by electrochemically assisted photocatalytic degradation of methyl orange. The results of XPS revealed that N and S were incorporated into the lattice of TiO2. FESEM showed that surface roughness and thickness of films varies depending on surface treatment. Voltammetric and XPS characterization of N-S co-doped TiO2 films supported on stainless steel revealed that their surface contains alpha-Fe2O3/FeOOH. Accordingly, iron contamination of the films coming from stainless steel was detrimental to the degradation of methyl orange. Prior to sol-gel coating process, sandblasting followed by nitric acid passivation for stainless steel or hydrofluoric acid pickling process in the case of titanium improved the PCA of N-S co-doped TiO2 films.

  12. Reaction pathways of biomass-derived oxygenates on noble metal surfaces

    NASA Astrophysics Data System (ADS)

    McManus, Jesse R.

    As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway

  13. Developing high-sensitivity ethanol liquid sensors based on ZnO/porous Si nanostructure surfaces using an electrochemical impedance technique

    NASA Astrophysics Data System (ADS)

    Husairi, Mohd; Rouhi, Jalal; Alvin, Kevin; Atikah, Zainurul; Rusop, Muhammad; Abdullah, Saifollah

    2014-07-01

    ZnO nanostructures were synthesized on porous Si (PSi) substrates using the thermal catalytic-free immersion method. Crack-like ZnO nanostructures were formed on the bare, sponge-like PSi structures. An approach to fabricate chemical sensors based on the ZnO/PSi nanostructure arrays that uses an electrochemical impedance technique is reported. Sensor performance was evaluated for ethanol solutions by the morphology and defect structures of the ZnO nanostructure layer. Results indicate that the ZnO/PSi nanostructure chemical sensor exhibits rapid and high response to ethanol compared with a PSi nanostructure sensor because of its small particle size and an oxide layer acting as a capacitive layer on the PSi nanostructure surface.

  14. Development, fabrication and evaluation of a novel biomimetic human breast tissue derived breast implant surface.

    PubMed

    Barr, S; Hill, E W; Bayat, A

    2017-02-01

    Breast implant use has tripled in the last decade with over 320,000 breast implant based reconstructions and augmentations performed in the US per annum. Unfortunately a considerable number of women will experience capsular contracture, the irrepressible and disfiguring, tightening and hardening of the fibrous capsule that envelops the implant. Functionalising implant surfaces with biocompatible tissue-specific textures may improve in vivo performance. A novel biomimetic breast implant is presented here with anti-inflammatory in vitro abilities. Topographical assessment of native breast tissue facilitated the development of a statistical model of adipose tissue. 3D grayscale photolithography and ion etching were combined to successfully replicate a surface modelled upon the statistics of breast tissue. Pro-inflammatory genes ILβ1, TNFα, and IL6 were downregulated (p<0.001) and anti-inflammatory gene IL-10 were upregulated on the novel surface. Pro-inflammatory cytokines Gro-Alpha, TNFα and neutrophil chemoattractant IL8 were produced in lower quantities and anti-inflammatory IL-10 in higher quantities in culture with the novel surface (p<0.01). Immunocytochemistry and SEM demonstrated favourable fibroblast and macrophage responses to these novel surfaces. This study describes the first biomimetic breast tissue derived breast implant surface. Our findings attest to its potential translational ability to reduce the inflammatory phase of the implant driven foreign body reaction.

  15. Surface nanotopography guides kidney-derived stem cell differentiation into podocytes.

    PubMed

    MacGregor-Ramiasa, Melanie; Hopp, Isabel; Bachhuka, Akash; Murray, Patricia; Vasilev, Krasimir

    2017-02-21

    Stem cells have enormous potential for developing novel therapies for kidney disease but our current inability to direct their differentiation to specialised renal cells presents a barrier to their use in renal bioengineering and drug development programmes. Here, a plasma-based technology was used to produce a range of biocompatible substrates comprising controlled surface nanotopography and tailored outermost chemical functionalities. These novel substrata were used to investigate the response of mouse kidney-derived stem cells to changes in both substrate nanotopography and surface chemistry. The stem cells proliferated to a similar extent on all substrates, but specific combinations of nanotopography and surface chemistry promoted differentiation into either podocyte or proximal tubule-like cells. The data reveal that high density of surface nanodefects in association with amine rich chemistry primarily lead to differentiation into podocytes while surfaces with low amine content constituted better substrates for differentiation into proximal tubule cells regardless of the surface nanotopographic profile. Thus plasma coated nanorough substrate may provide useful platform for guiding the fate kidney stem cell in vitro.

  16. Electrochemical synthesis of nanostructured materials for electrochemical energy conversion and storage.

    PubMed

    Li, Gao-Ren; Xu, Han; Lu, Xue-Feng; Feng, Jin-Xian; Tong, Ye-Xiang; Su, Cheng-Yong

    2013-05-21

    Electrochemical synthesis represents a highly efficient method for the fabrication of nanostructured energy materials, and various nanostructures, such as nanorods, nanowires, nanotubes, nanosheets, dendritic nanostructures, and composite nanostructures, can be easily fabricated with advantages of low cost, low synthetic temperature, high purity, simplicity, and environmental friendliness. The electrochemical synthesis, characterization, and application of electrochemical energy nanomaterials have advanced greatly in the past few decades, allowing an increasing understanding of nanostructure-property-performance relationships. Herein, we highlight some recent progress in the electrochemical synthesis of electrochemical energy materials with the assistance of additives and templates in solution or grafted onto metal or conductive polymer supports, with special attention to the effects on surface morphologies, structures and, more importantly, electrochemical performance. The methodology for preparing novel electrochemical energy nanomaterials and their potential applications has been summarized. Finally, we outline our personal perspectives on the electrochemical synthesis and applications of electrochemical energy nanomaterials.

  17. Three-dimensional surface deformation derived from airborne interferometric UAVSAR: Application to the Slumgullion Landslide

    NASA Astrophysics Data System (ADS)

    Delbridge, Brent G.; Bürgmann, Roland; Fielding, Eric; Hensley, Scott; Schulz, William H.

    2016-05-01

    In order to provide surface geodetic measurements with "landslide-wide" spatial coverage, we develop and validate a method for the characterization of 3-D surface deformation using the unique capabilities of the Uninhabited Aerial Vehicle Synthetic Aperture Radar (UAVSAR) airborne repeat-pass radar interferometry system. We apply our method at the well-studied Slumgullion Landslide, which is 3.9 km long and moves persistently at rates up to ˜2 cm/day. A comparison with concurrent GPS measurements validates this method and shows that it provides reliable and accurate 3-D surface deformation measurements. The UAVSAR-derived vector velocity field measurements accurately capture the sharp boundaries defining previously identified kinematic units and geomorphic domains within the landslide. We acquired data across the landslide during spring and summer and identify that the landslide moves more slowly during summer except at its head, presumably in response to spatiotemporal variations in snowmelt infiltration. In order to constrain the mechanics controlling landslide motion from surface velocity measurements, we present an inversion framework for the extraction of slide thickness and basal geometry from dense 3-D surface velocity fields. We find that the average depth of the Slumgullion Landslide is 7.5 m, several meters less than previous depth estimates. We show that by considering a viscoplastic rheology, we can derive tighter theoretical bounds on the rheological parameter relating mean horizontal flow rate to surface velocity. Using inclinometer data for slow-moving, clay-rich landslides across the globe, we find a consistent value for the rheological parameter of 0.85 ± 0.08.

  18. A Multiyear Dataset of SSM/I-Derived Global Ocean Surface Turbulent Fluxes

    NASA Technical Reports Server (NTRS)

    Chou, Shu-Hsien; Shie, Chung-Lin; Atlas, Robert M.; Ardizzone, Joe; Nelkin, Eric; Einaudi, Franco (Technical Monitor)

    2001-01-01

    The surface turbulent fluxes of momentum, latent heat, and sensible heat over global oceans are essential to weather, climate and ocean problems. Evaporation is a key component of the hydrological cycle and the surface heat budget, while the wind stress is the major forcing for driving the oceanic circulation. The global air-sea fluxes of momentum, latent and sensible heat, radiation, and freshwater (precipitation-evaporation) are the forcing for driving oceanic circulation and, hence, are essential for understanding the general circulation of global oceans. The global air-sea fluxes are required for driving ocean models and validating coupled ocean-atmosphere global models. We have produced a 7.5-year (July 1987-December 1994) dataset of daily surface turbulent fluxes over the global oceans from the Special Sensor microwave/Imager (SSM/I) data. Daily turbulent fluxes were derived from daily data of SSM/I surface winds and specific humidity, National Centers for Environmental Prediction (NCEP) sea surface temperatures, and European Centre for Medium-Range Weather Forecasts (ECMWF) air-sea temperature differences, using a stability-dependent bulk scheme. The retrieved instantaneous surface air humidity (with a 25-km resolution) validated well with that of the collocated radiosonde observations over the global oceans. Furthermore, the retrieved daily wind stresses and latent heat fluxes were found to agree well with that of the in situ measurements (IMET buoy, RV Moana Wave, and RV Wecoma) in the western Pacific warm pool during the TOGA COARE intensive observing period (November 1992-February 1993). The global distributions of 1988-94 seasonal-mean turbulent fluxes will be presented. In addition, the global distributions of 1990-93 annual-means turbulent fluxes and input variables will be compared with those of UWM/COADS covering the same period. The latter is based on the COADS (comprehensive ocean-atmosphere data set) and is recognized to be one of the best

  19. Molecular structure of substituted phenylamine alpha-OMe- and alpha-OH-p-benzoquinone derivatives. Synthesis and correlation of spectroscopic, electrochemical, and theoretical parameters.

    PubMed

    Aguilar-Martínez, M; Bautista-Martínez, J A; Macías-Ruvalcaba, N; González, I; Tovar, E; Marín del Alizal, T; Collera, O; Cuevas, G

    2001-12-14

    Thirteen C(6) para-substituted anilinebenzoquinones derived from perezone (PZ) (2-(1,5-dimethyl-4-hexenyl)-3-hydroxy-5-methyl-1,4-benzoquinone) were prepared to analyze the effect of the substituents on quinone electronic properties. The effect of a hydrogen bond between the alpha-hydroxy and carbonyl C(4)-O(4) groups was determined in perezone derivatives by substituting electron-donor and electron-acceptor groups such as -OMe, -Me, -Br, and -CN and comparing the -OH (APZs) and -OMe (APZms) derivatives. Reduction potentials of these compounds were measured using cyclic voltammetry in anhydrous acetonitrile. The typical behavior of quinones, with or without alpha-phenolic protons, in an aprotic medium was not observed for APZs due to the presence of coupled, self-protonation reactions. The self-protonation process gives rise to an initial wave, corresponding to the irreversible reduction reaction of quinone (HQ) to hydroquinone (HQH(2)), and to a second electron transfer, attributed to the reversible reduction of perezonate (Q(-)) formed during the self-protonation process. This reaction is favored by the acidity of the alpha-OH located at the quinone ring. To control the coupled chemical reaction, we considered both methylation of the -OH group (APZms) and addition of a strong base, tetramethylammonium phenolate (Me(4)N(+)C(6)H(5)O(-)), to completely deprotonate the APZs. Methylation led to recovery of reversible, bi-electronic behavior (Q/Q(*)(-) and Q(*)(-)/Q(2)(-)), indicating the nonacidic properties of the NH group. The addition of a strong base resulted in reduction of perezonate (Q(-)) obtained from the acid-base reaction of APZs with Me(4)N(+)C(6)H(5)O(-) to produce the dianion radical (Q(*)(2)(-)). Although the nitrogen atom interferes with direct conjugation between both rings by binding the quinone with the para-substituted ring, the UV-vis spectra of these compounds showed the existence of intramolecular electronic transfer from the respective aniline

  20. Seeded-growth approach to fabrication of silver nanoparticle films on silicon for electrochemical ATR surface-enhanced IR absorption spectroscopy.

    PubMed

    Huo, Sheng-Juan; Xue, Xiao-Kang; Li, Qiao-Xia; Xu, Su-Fan; Cai, Wen-Bin

    2006-12-28

    Ag nanoparticle films (simplified as nanofilms hereafter) on Si for electrochemical ATR surface enhanced IR absorption spectroscopy (ATR-SEIRAS) have been successfully fabricated by using chemical deposition, which incorporates initial embedding of Ag seeds on the reflecting plane of an ATR Si prism and subsequent chemical plating of conductive and SEIRA-active Ag nanofilms. Two alternative methods for embedding initial Ag seeds have been developed: one is based on self-assembly of Ag colloids on an aminosilanized Si surface, whereas the other the reduction of Ag+ in a HF-containing solution. A modified silver-mirror reaction was employed for further growth of Ag seeds into Ag nanofilm electrodes with a theoretically average thickness of 40-50 nm. Both Ag seeds and as-deposited Ag nanofilms display island structure morphologies facilitating SEIRA, as revealed by AFM imaging. The cyclic voltammetric feature of the as-prepared Ag nanofilm electrodes is close to that of a polycrystalline bulk Ag electrode. With thiocyanate as a surface probe, enhancement factors of ca. 50-80 were estimated for the as-deposited Ag nanofilms as compared to a mechanically polished Ag electrode in the conventional IRAS after reasonable calibration of surface roughness factor, incident angles, surface coverage, and polarization states. As a preliminary example for extended application, the pyridine adsorption configuration at an as-deposited Ag electrode was re-examined by ATR-SEIRAS. The results revealed that pyridine molecules are bound via N end to the Ag electrode with its ring plane perpendicular or slightly tilted to the local surface without rotating its C2 axis about the surface normal, consistent with the conclusion drawn by SERS in the literature.

  1. Optimisation of the hot conditioning of carbon steel surfaces of primary heat transport system of Pressurized Heavy Water Reactors using electrochemical impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Kiran Kumar, M.; Gaonkar, Krishna; Ghosh, Swati; Kain, Vivekanand; Bojinov, Martin; Saario, Timo

    2010-06-01

    Hot conditioning operation of the primary heat transport system is an important step prior to the commissioning of Pressurized Heavy Water Reactors. One of the major objectives of the operation is to develop a stable and protective magnetite layer on the inner surfaces of carbon steel piping. The correlation between stable magnetite film growth on carbon steel surfaces and the period of exposure to hot conditioning environment is generally established by a combination of weight change measurements and microscopic/morphological observations of the specimens periodically removed during the operation. In the present study, electrochemical impedance spectroscopy (EIS) at room temperature is demonstrated as an alternate, quantitative technique to arrive at an optimal duration of the exposure period. Specimens of carbon steel were exposed for 24, 35 and 48 h during hot conditioning of primary heat transport system of two Indian PHWRs. The composition and morphology of oxide films grown during exposure was characterized by X-ray diffraction and optical microscopy. Further, ex situ electrochemical impedance spectra of magnetite films formed after each exposure were measured, in 1 ppm Li + electrolyte at room temperature as a function of potential in a range of -0.8 to +0.3 VSCE. The defect density of the magnetite films formed after each exposure was estimated by Mott-Schottky analysis of capacitances extracted from the impedance spectra. Further the ionic resistance of the oxide was also extracted from the impedance spectra. Defect density was observed to decrease with increase in exposure time and to saturate after 35 h, indicating stabilisation of the barrier layer part of the magnetite film. The values of the ionic transport resistance start to increase after 35-40 h of exposure. The quantitative ability of EIS technique to assess the film quality demonstrates that it can be used as a supplementary tool to the thickness and morphological characterizations of samples

  2. Novel ball-type four dithioerythritol bridged metallophthalocyanines and their water-soluble derivatives: Synthesis and characterization, and electrochemical, electrocatalytic, electrical and gas sensing properties.

    PubMed

    Ceyhan, Tanju; Altındal, Ahmet; Ozkaya, Ali Rıza; Salih, Bekir; Bekaroğlu, Ozer

    2010-11-07

    The phthalodinitrile derivative 3 was prepared by the reaction of 1,4-dithioerythritol 1 and 4-nitrophthalonitrile 2 in dry DMF as the solvent in the presence of K(2)CO(3) as the base by the method of nucleophilic substitution of an activated nitro group in an aromatic ring. The template reaction of compound 3 with the corresponding metal salts gave the novel binuclear MPcs of ball-type (M = Zn 4, Co 5, Cu 6) and their water soluble phthalocyanines 7-9 were obtained from refluxing a suspension of the compounds bearing eight OH side groups, in aqueous NaOH (%30) solution. Newly synthesized compounds were characterized by elemental analysis, UV/VIS, IR, MALDI TOF mass and (1)H-NMR spectroscopy techniques. The electronic spectra exhibit an intense π→π* transition of characteristic Q and B bands of the phthalocyanine core. The electrochemical measurements showed the formation of various mixed-valence oxidation and reduction species of 4 and 6 due to weak intramolecular interactions between the two MPc units. Complex 5 displayed a much higher catalytic activity than those of 4 and 6. It was found that oxygen reduction on the 5-based catalyst occurs through a direct 4-electron transfer pathway with a high water selectivity. However, the overpotential for oxygen reduction is high, probably due to a long distance between the two CoPc units in 5. A.c. and d.c. conductivity measurements were performed as a function of temperature (300-543 K) and frequency (40-10(5) Hz). It was found from d.c. measurements that the values of the pre-exponential factor σ(0) for the investigated samples are in the interval from 1.36 × 10(-3) to 6.20 × 10(2)Ω(-1) cm(-1), inferring that the conduction occurs most probably by hopping between the localized states in band tails. Based on the existing theory of a.c. conduction, it has been concluded that for the low frequency region the dominant conduction mechanism is multihopping at high temperatures (>390 K) whereas for the high frequency

  3. Cloud fields derived from satellite and surface data during FIRE cirrus phase 2

    NASA Technical Reports Server (NTRS)

    Minnis, Patrick; Smith, William L., Jr.; Young, David F.; Heck, Patrick W.

    1993-01-01

    The interpretation of surface and aircraft measurements of cloud properties taken during field programs must take into account the large-scale cloud and meteorological conditions. Cloud properties are also required at scales beyond the point and line data taken from ground and aircraft platforms. Satellite data can provide a quantitative description of these large-scale cloud properties. When derived from geostationary satellite data, the cloud fields constitute a unique source for evaluating the development and demise of a cloud system. Satellites, however, can only see the tops of clouds, so that cloud layers below the uppermost cloud deck may remain undetected resulting in a incomplete depiction of the cloud system. Some multilayer clouds are amenable to detection from satellites. Many, especially in midlatitude cyclonic systems, can only be observed from the surface. A combination of surface and satellite cloud observations should be the most complete quantification of large-scale cloudiness if there are sufficient surface measurements. During the First International Satellite Cloud Climatology Project (ISCCP) Regional Experiment Phase 2 (FIRE-2) Cirrus Intensive Field Observation (IFO) period (November 13 - December 7, 1991) conducted at Coffeyville, Kansas, cirrus observations were taken in a variety of conditions. The IFO area was selected for a variety of reasons including the relatively dense network of surface weather stations and special surface instrumentation sites. Thus, the FIRE-2 IFO presents an excellent opportunity to combine cloud observations from surface and satellite observations. This paper presents an analysis of cloud properties on a mesoscale grid using satellite cloud property retrievals, surface observer data, and rawinsonde temperature and humidity profiles.

  4. Effect of nano-structured bioceramic surface on osteogenic differentiation of adipose derived stem cells.

    PubMed

    Xia, Lunguo; Lin, Kaili; Jiang, Xinquan; Fang, Bing; Xu, Yuanjin; Liu, Jiaqiang; Zeng, Deliang; Zhang, Maolin; Zhang, Xiuli; Chang, Jiang; Zhang, Zhiyuan

    2014-10-01

    Tissue engineering strategies to construct vascularized bone grafts potentially revolutionize the treatment of massive bone loss. The surface topography of the grafts plays critical roles on bone regeneration, while adipose derived stem cells (ASCs) are known for their capability to promote osteogenesis and angiogenesis when applied to bone defects. In the present study, the effects of hydroxyapatite (HAp) bioceramic scaffolds with nanosheet, nanorod, and micro-nano-hybrid (the hybrid of nanorod and microrod) surface topographies on attachment, proliferation and osteogenic differentiation, as well as the expression of angiogenic factors of rat ASCs were systematically investigated. The results showed that the HAp bioceramic scaffolds with the micro-/nano-topography surfaces significantly enhanced cell attachment and viability, alkaline phosphatase (ALP) activity, and mRNA expression levels of osteogenic markers and angiogenic factors of ASCs. More importantly, the biomimetic feature of the hierarchical micro-nano-hybrid surface topography showed the highest stimulatory effect. The activation in Akt signaling pathway was observed in ASCs cultured on HAp bioceramics with nanorod, and micro-nano-hybrid surface topographies. Moreover, these induction effects could be repressed by Akt signaling pathway inhibitor LY294002. Finally, the in vivo bone regeneration results of rat critical-sized calvarial defect models confirmed that the combination of the micro-nano-hybrid surface and ASCs could significantly enhance both osteogenesis and angiogenesis as compared with the control HAp bioceramic scaffold with traditional smooth surface. Our results suggest that HAp bioceramic scaffolds with micro-nano-hybrid surface can act as cell carrier for ASCs, and consequently combine with ASCs to construct vascularized tissue-engineered bone.

  5. Using a scoop to derive soil mechanical parameters on the surface of Mars

    NASA Astrophysics Data System (ADS)

    Kargl, Günter; Poganski, Joshua; Kömle, Norbert I.; Schweiger, Helmut; Macher, Wolfgang

    2016-04-01

    We will report on the possibility of using the scoop attached to the instrument deployment arm to perform soil mechanical experiments directly on the surface of Mars. The Phoenix mission flown 2009 had an instrument deployment arm which was also used to sample surface material indo instruments mounted on the lander deck. The flight spare of this arm will again be flown to Mars on board the InSight mission. Although, the primary purpose of the arm and the attached scoop was not soil mechanical investigations it was already demonstrated by the Phoenix mission that the arm can be used to perform auxiliary investigations of the surface materials. We will report on modelling efforts using a Discrete Element Software package to demonstrate that simple soil mechanical experiments can be used to derive essential material parameters like e.g. angle of repose and others. This is of particular interest since it would be possible to implement experiments using the hardware of the InSight mission. PIC Cross section cut through a trench dug out by the scoop and the pile of the deposed material which both can be used to derive soil mechanical parameters.

  6. Use of cellulose derivatives on gold surfaces for reduced nonspecific adsorption of immunoglobulin G.

    PubMed

    Volden, Sondre; Zhu, Kaizheng; Nyström, Bo; Glomm, Wilhelm R

    2009-09-01

    This study addresses the design of protein-repellent gold surfaces using hydroxyethyl- and ethyl(hydroxyethyl) cellulose (HEC and EHEC) and hydrophobically modified analogues of these polymers (HM-HEC and HM-EHEC). Adsorption behavior of the protein immunoglobulin G (IgG) onto pure gold and gold surfaces coated with cellulose polymers was investigated and described by quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM) and contact angle measurements (CAM). Surfaces coated with the hydrophobically modified cellulose derivatives were found to significantly outperform a reference poly(ethylene glycol) (PEG) coating, which in turn prevented 90% of non-specific protein adsorption as compared to adsorption onto pure gold. HEC and EHEC prevented around 30% and 60% of the IgG adsorption observed on pure gold, while HM-HEC and HM-EHEC were both found to completely hinder biofouling when deposited on the gold substrates. Adsorption behavior of IgG has been discussed in terms of polymer surface coverage and roughness of the applied surfaces, together with hydrophobic interactions between protein and gold, and also polymer-protein interactions.

  7. Enhanced biofouling resistance of polyethersulfone membrane surface modified with capsaicin derivative and itaconic acid

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Gao, Xueli; Wang, Qun; Sun, Haijing; Wang, Xiaojuan; Gao, Congjie

    2015-11-01

    The culprit of biofouling is the reproduction of viable microorganisms on the membrane surface. Recently, functionalization of membrane surface with natural antibacterial agents has drawn great attention. This work presents the fabrication of antibiofouling polyethersulfone (PES) ultrafiltration (UF) membranes by UV-assisted photo grafting of capsaicin derivative (N-(4-hydroxy-3-methoxy-benzyl)-acrylamide, HMBA) and itaconic acid (IA) on the surface of PES membrane. Results of FTIR-ATR, water static contact angle (WSCA) and atomic force microscopy (AFM) analysis confirmed the successful grafting of HMBA and IA on the membrane surface. We investigated the antifouling and antibacterial properties of these membranes using BSA and Escherichia coli as the test model, respectively. During a 150-min test, the modified membranes show much lower flux decline (42.7% for PES-g-1H0I, 22.2% for PES-g-1H1I and 7.7% for PES-g-1H5I) when compared with the pristine membrane (flux declined by 77%). The modified membranes exhibit excellent antibacterial activity (nearly 100%) when UV irradiation time was 6 min. The morphological study suggested that the E. coli on the pristine membrane showed a regular and smooth surface while that on the modified membrane was disrupted, which validated the antibacterial activity of the modified membranes.

  8. Twist-bulge derivatives and deformations of convex real projective structures on surfaces

    NASA Astrophysics Data System (ADS)

    Long, Terence

    Let S be a closed orientable surface with genus g > 1 equipped with a convex RP2 structure. A basic example of such a convex $RP2 structure on a surface S is the one associated to a hyperbolic structure on S, and in this special case Wolpert proved formulas for computing the Lie derivatives talpha lbeta and tgamma talphal, where t alpha is the Fenchel-Nielsen twist vector field associated to the twist along a geodesic alpha, and l* is the hyperbolic geodesic length function. In this dissertation, we extend Wolpert's calculation of talphal beta and tgammat alphabeta in the hyperbolic setting to the case of convex real projective surfaces; in particular, our t alpha is the twist-bulge vector field along geodesic alpha coming from the parametrization of the deformation space of convex RP 2 structures on a surface due to Goldman, and our geodesic length function l* is in terms of a generalized cross-ratio in the sense of Labourie. To this end, we use results due to Labourie and Fock-Goncharov on the existence of an equivariant flag curve associated to Hitchin representations, of which convex real projective surfaces are an example. This flag curve allows us to extend the notions arising in the hyperbolic case to that of convex real projective structures and to complete our generalization of Wolpert's formulas.

  9. Seasonal variation of surface and atmospheric cloud radiative forcing over the globe derived from satellite data

    NASA Technical Reports Server (NTRS)

    Gupta, Shashi K.; Staylor, W. Frank; Darnell, Wayne L.; Wilber, Anne C.; Ritchey, Nancy A.

    1993-01-01

    Global distributions of surface and atmospheric cloud radiative forcing parameters have been derived using parameterized radiation models with satellite meteorological data from the International Satellite Cloud Climatology Project, and directly measured top-of-atmosphere radiative fluxes from the Earth Radiation Budget Experiment. Specifically, shortwave, longwave, and total cloud forcing at the surface, and column-averaged values of longwave cloud forcing of the atmosphere were derived for the midseasonal months of April, July, and October 1985 and January 1986, covering a complete annual cycle. Seasonal variability is illustrated by comparing the results for July 1985 and January 1986, which represent the seasonal extremes. Surface shortwave cloud forcing is always negative, representing a cooling of the surface, with strongest cooling (-120 to -180 W/sq m) occurring over midlatitude storm tracks of the summer hemisphere. Surface longwave cloud forcing is always positive, representing a warming of the surface, with strongest warming (60 to 75 W/sq m) occurring over storm tracks of the winter hemisphere. Zonal averages show the entire summer hemisphere dominated by shortwave cooling, the middle and high latitudes of the winter hemisphere dominated by longwave warming, and a broad zone of transition in between. The globally averaged total cloud forcing amounts to a cooling throughout the year, ranging from a low of about -12 W/sq m for July 1985 to a high of about -25 W/sq m for January 1986. The longwave cloud forcing of the atmosphere shows a strong warming over deep convective regions in the tropics and a moderate cooling outside the tropics, amounting to a weak cooling (-2 to -5 W/sq m) in the global average. Comparisons of the results with general circulation model simulations show broad qualitative agreement regarding the locations of prominent warming and cooling regions. Quantitative comparisons, on the other hand, show significant differences between the

  10. Alkaloids extract of Retama monosperma (L.) Boiss. seeds used as novel eco-friendly inhibitor for carbon steel corrosion in 1 M HCl solution: Electrochemical and surface studies

    NASA Astrophysics Data System (ADS)

    El Hamdani, Naoual; Fdil, Rabiaa; Tourabi, Mustapha; Jama, Charafeddine; Bentiss, Fouad

    2015-12-01

    Current research efforts now focus on the development of non-toxic, inexpensive and environmentally friendly corrosion inhibitors as alternatives to different organic and non-organic compounds. In this field, alkaloids extract of Retama monosperma (L.) Boiss. seeds (AERS) was tested for the first time as corrosion inhibitor for carbon steel in 1 M HCl medium using electrochemical and surface characterization techniques. The obtained results showed that this plant extract's acts as an efficient corrosion inhibitor for carbon steel in 1 M HCl and an inhibition efficiency of 94.4% was reached with 400 mg/L of AERS at 30 °C. Ac impedance experimental data revealed a frequency distribution of the capacitance, simulated as constant phase element. Impedance results demonstrated that the addition of the AERS in the corrosive solution decreases the charge capacitance and simultaneously increases the function of the charge/discharge of the interface, facilitating the formation of an adsorbed layer over the steel surface. Polarization curves indicated that AERS is a mixed inhibitor. Adsorption of such alkaloid extract on the steel surface obeyed to the Langmuir adsorption isotherm. X-ray photoelectron spectroscopy (XPS) showed that the inhibition of steel corrosion in normal hydrochloric solution by AERS is mainly controlled by a physisorption process and the inhibitive layer is composed of an iron oxide/hydroxide mixture where AERS molecules are incorporated.

  11. Electrochemical sensor for monitoring electrochemical potentials of fuel cell components

    DOEpatents

    Kunz, Harold R.; Breault, Richard D.

    1993-01-01

    An electrochemical sensor comprised of wires, a sheath, and a conduit can be utilized to monitor fuel cell component electric potentials during fuel cell shut down or steady state. The electrochemical sensor contacts an electrolyte reservoir plate such that the conduit wicks electrolyte through capillary action to the wires to provide water necessary for the electrolysis reaction which occurs thereon. A voltage is applied across the wires of the electrochemical sensor until hydrogen evolution occurs at the surface of one of the wires, thereby forming a hydrogen reference electrode. The voltage of the fuel cell component is then determined with relation to the hydrogen reference electrode.

  12. Electrochemical cell

    DOEpatents

    Redey, Laszlo I.; Vissers, Donald R.; Prakash, Jai

    1994-01-01

    An electrochemical cell having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm.sup.3 ; the cell can be 90% recharged in three hours and can operate at temperatures below 160.degree. C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6.times.10.sup.4 cm.sup.2 /g of Ni.

  13. Electrochemical cell

    DOEpatents

    Redey, Laszlo I.; Vissers, Donald R.; Prakash, Jai

    1996-01-01

    An electrochemical cell having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm.sup.3 ; the cell can be 90% recharged in three hours and can operate at temperatures below 160.degree. C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6.times.10.sup.4 cm.sup.2 /g of Ni.

  14. Electrochemical cell

    DOEpatents

    Redey, L.I.; Vissers, D.R.; Prakash, J.

    1996-07-16

    An electrochemical cell is described having a bimodal positive electrode, a negative electrode of an alkali metal, and a compatible electrolyte including an alkali metal salt molten at the cell operating temperature. The positive electrode has an electrochemically active layer of at least one transition metal chloride at least partially present as a charging product, and additives of bromide and/or iodide and sulfur in the positive electrode or the electrolyte. Electrode volumetric capacity is in excess of 400 Ah/cm{sup 3}; the cell can be 90% recharged in three hours and can operate at temperatures below 160 C. There is also disclosed a method of reducing the operating temperature and improving the overall volumetric capacity of an electrochemical cell and for producing a positive electrode having a BET area greater than 6{times}10{sup 4}cm{sup 2}/g of Ni. 6 figs.

  15. Electrochemical cell

    DOEpatents

    Redey, L.I.; Vissers, D.R.; Prakash, J.

    1994-02-01

    A