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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. The Synthesis of Diquinone and Dihydroquinone Derivatives of Calix[4]arene and Electrochemical Characterization on Au(111) surface.

    PubMed

    Genorio, Boštjan

    2016-01-01

    Several new electroactive diquinone and dihydroquinone derivatives of calix[4]arene bearing anchor functional groups were designed, synthesized and characterized. A method for selective protection of the hydroquinone -OH groups with trimethylsilyl groups (TMS) either on lower-rim or on upper-rim was developed. Four selected molecules - with sulfide anchor groups and carboxylic anchor groups - were adsorbed onto Au(111) single crystal surface using ex-situ and insitu self-assembly methods. Adsorbed molecules were then electrochemically probed with cyclic voltammetry. All adsorbed molecules showed redox response which changed during cycling. After conditioning CVs stabilized and showed two distinct current peaks for all molecules. Synthesized and electrochemically probed molecules are of interest to: Li-ion batteries (as cathode materials and overcharge protection), beyond Li-ion batteries and redox-flow batteries. PMID:27640377

  3. Carbohydrate derivative-functionalized biosensing toward highly sensitive electrochemical detection of cell surface glycan expression as cancer biomarker.

    PubMed

    Zhang, Xinai; Lu, Wenjie; Shen, Jianzhong; Jiang, Yuxiang; Han, En; Dong, Xiaoya; Huang, Jiali

    2015-12-15

    Accurate and highly sensitive detection of glycan expression on cell surface is extremely important for cancer diagnosis and therapy. Herein, a carbohydrate derivative-functionalized biosensor was developed for electrochemical detection of the expression level of cell surface glycan (mannose used as model). Thiomannosyl dimer was synthesized to design the thiomannosyl-functionalized biosensor by direct and rapid one-step protocols. The biosensing surface-confined mannose could effectively mimic the presentation of cell surface mannose and was responsible for competing with mannose on cancer cells in incubation solution. Greatly enhanced sensitivity was achieved by exploiting the excellent conductivity of multiwalled carbon nanotube/Au nanoparticle (MWNT/AuNP), the amplification effect of MWNTs, and the favorable catalytic ability of horseradish peroxidase (HRP). Using competitive strategy, the developed biosensor exhibits attractive performances for the analysis of mannose expression with rapid response, high sensitivity and accuracy, and possesses great promise for evaluation of cell surface glycan expression by using a greater variety of lectins.

  4. 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.

  5. 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.

  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. 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.

  8. 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-.

  9. Electrochemical studies on surface coated LiCoVO 4 with Al 2O 3 derived from carboxylate-alumoxane for lithium-ion cells

    NASA Astrophysics Data System (ADS)

    Fey, George Ting-Kuo; Muralidharan, P.; Cho, Yung-Da

    Various wt.% of Al 2O 3 derived from methoxyethoxy-alumoxane (MEA-alumoxane) were coated by a simple mechano-thermal method on the LiCoVO 4 particles, which were synthesized by a citric acid-urea polymeric method. Powder XRD patterns confirmed that the prepared LiCoVO 4 crystalline sample had an inverse spinel structure when heated at 773 K for 5 h in air and the LiCoVO 4 materials coated with Al 2O 3 showed no evidence of secondary phase peaks. TEM images of LiCoVO 4 identified that the nanosized particles ranged ∼100-120 nm and Al 2O 3 coating had an average thickness of ∼20 nm over the fine particle of LiCoVO 4. XPS binding energy data indicated that the presence of two different types O 1s ions corresponds to alumina and core LiCoVO 4 material. The charge and discharge study indicated that the 0.5 wt.% Al 2O 3 derived from MEA-alumoxane coated material delivered an initial discharge capacity of 68 mAh g -1 at 3.0-4.5 V and the cycle stability after 20 cycles was stable without any drastic capacity fade normally exhibited by inverse spinel materials. The d Q/d V versus voltage plots revealed that the slower impedance growth for the Al 2O 3 surface coated LiCoVO 4 cathode material.

  10. Electrochemical Potential Derived from Atomic Cluster Structures.

    PubMed

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

    2016-02-01

    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. PMID:26801811

  11. Electrochemical Potential Derived from Atomic Cluster Structures.

    PubMed

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

    2016-02-01

    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. Surface electrochemical control for fine coal and pyrite separation

    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.

    1991-01-01

    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 covers a Raman spectroscopy of species produced electrochemically on pyrite surfaces.

  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. Spectral, electrochemical and thermal characteristics of glass forming hydrazine derivatives

    NASA Astrophysics Data System (ADS)

    Bijak, Katarzyna; Sek, Danuta; Siwy, Mariola; Grucela-Zajac, Marzena; Janeczek, Henryk; Wiacek, Malgorzata; Malecki, Grzegorz; Schab-Balcerzak, Ewa

    2014-11-01

    The azines being condensation products of benzophenone hydrazone with triphenylamine substituted with different numbers of aldehyde groups and also with terephthaldicarboxaldehyde were prepared. Their spectral, thermal and electronic properties that is, orbital energies and resulting energy gap calculated theoretically by density functional theory (DFT) and estimated by electrochemical measurements were explored. The prepared hydrazine derivatives exhibited glass-forming properties with glass-transition temperatures in the range of 10-98 °C and high thermal stability with decomposition temperatures placed between 231 and 337 °C. The photoluminescence (PL) studies showed that all investigated compounds both in solid state as blends with PMMA and in NMP solution emitted blue light, however, with different intensity. Relative PL intensity of azines was investigated in NMP in relation to rhodamine-B used as a standard. Moreover, the stability of azines during doping with acid and ferric chloride was spectroscopically demonstrated via repeated doping/dedoping in solution and in film. All compounds are electrochemically active. Depend on chemical structure of azines they undergo reversible or irreversible electrochemical oxidation and reduction processes. The LUMO levels were found in the range from -2.66 to -3.0 eV. They exhibited energy band gap (Eg) estimated electrochemically from 2.57 to 3.22 eV.

  16. 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.

  17. An electrochemically switched smart surface for peptide immobilization and conformation control.

    PubMed

    Li, Jun; Sun, Chun-Lin; Shen, Rong; Cao, Xiao-Yan; Zhou, Bo; Bai, De-Cheng; Zhang, Hao-Li

    2014-08-01

    We report an electrochemically switched smart surface for controlled peptide immobilization and conformation control. This dynamic surface is based on self-assembled monolayers (SAMs) containing surface-bound trimethoxybenzene moieties, which can undergo electrochemically modulated surface activation to be stepwisely converted to two catechol derivatives. This new smart surface can be used to realize stepwise immobilization of a peptide, and more importantly, to control peptide conformation on a surface. We demonstrate herein that with one electrochemical activation step, a linear peptide containing an RGD sequence can be attached onto the SAMs. With the subsequence activation step, the attached linear RGD peptide can be converted into cyclic conformation. The SAMs bounded with linear and cyclic RGD exhibit different adhesion behaviors to fibroblasts cells. The reaction procedure can be well-monitored by cyclic voltammetry (CV), electrochemical surface enhanced Raman microscopy (EC-SERS), and X-ray photoelectron spectroscopy (XPS). It is believed this robust smart surface can find wide applications in surface immobilization of bioactive moieties.

  18. Surface engineered porous silicon for stable, high performance electrochemical supercapacitors

    PubMed Central

    Oakes, Landon; Westover, Andrew; Mares, Jeremy W.; Chatterjee, Shahana; Erwin, William R.; Bardhan, Rizia; Weiss, Sharon M.; Pint, Cary L.

    2013-01-01

    Silicon materials remain unused for supercapacitors due to extreme reactivity of silicon with electrolytes. However, doped silicon materials boast a low mass density, excellent conductivity, a controllably etched nanoporous structure, and combined earth abundance and technological presence appealing to diverse energy storage frameworks. Here, we demonstrate a universal route to transform porous silicon (P-Si) into stable electrodes for electrochemical devices through growth of an ultra-thin, conformal graphene coating on the P-Si surface. This graphene coating simultaneously passivates surface charge traps and provides an ideal electrode-electrolyte electrochemical interface. This leads to 10–40X improvement in energy density, and a 2X wider electrochemical window compared to identically-structured unpassivated P-Si. This work demonstrates a technique generalizable to mesoporous and nanoporous materials that decouples the engineering of electrode structure and electrochemical surface stability to engineer performance in electrochemical environments. Specifically, we demonstrate P-Si as a promising new platform for grid-scale and integrated electrochemical energy storage. PMID:24145684

  19. 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.

  20. 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.

  1. 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.

  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. Electrochemical modification of Surface valence - Cr precipitates on LSCF surfaces

    NASA Astrophysics Data System (ADS)

    Finsterbusch, Martin; Schaefer, J. A.; Eigenbrodt, B. C.; Walker, R. A.; Lussier, A.; Idzerda, Y. U.

    2010-10-01

    Interactions of gaseous Cr contaminants with the perovskite material LSCF (La0.6Sr0.4Co0.2Fe0.8O3) commonly used as cathode for Solid Oxide Fuel Cells (SOFC) were investigated by means of X-ray absorption Spectroscopy (XAS) and Raman Spectroscopy. The setup consisted of a model cell with a GDC (Gd0.1Ce0.9O2) electrolyte pellet with a LSCF cathode on both sides in a Cr containing sample holder. The chemical structure and valency of the precipitate were found to depend on the electrochemical conditions of the surface, particularly on the bias voltage and not the total current density present in the cell. Cr^6+ spinels were found to form under high bias voltage, while under low bias voltage mostly Cr2O3 was formed. The influence of the contact material (Au vs. Ag) and the effect of quenching were investigated by Raman Spectroscopy under operating conditions (800 C in air). XAS unlike EDS, XRD or XPS is a precise and valuable tool for the direct measurement of the oxidation state of transition metals in compounds if the concentration is low (contamination) and the substrate is porous.

  4. Electrochemical Biosensors Based on Ferroceneboronic Acid and Its Derivatives: A Review

    PubMed Central

    Wang, Baozhen; Takahashi, Shigehiro; Du, Xiaoyan; Anzai, Jun-ichi

    2014-01-01

    We review recent progress in the development of electrochemical biosensors based on ferroceneboronic acid (FcBA) and ferrocene (Fc)-modified boronic acids. These compounds can be used to construct electrochemical biosensors because they consist of a binding site (i.e., a boronic acid moiety) and an electrochemically active part (i.e., an Fc residue). By taking advantage of the unique properties of FcBA and its derivatives, electrochemical sensors sensitive to sugars, glycated hemoglobin (HbA1c), fluoride (F−) ions, and so forth have been widely studied. FcBA-based sugar sensors rely on the selective binding of FcBA to 1,2- or 1,3-diol residues of sugars through the formation of cyclic boronate ester bonds. The redox properties of FcBA-sugar adduct differ from those of free FcBA, which forms the basis of the electrochemical determination of sugars. Thus, non-enzymatic glucose sensors are now being actively studied using FcBA and Fc-modified boronic acids as redox markers. Using a similar principle, HbA1c can be detected by FcBA-based electrochemical systems because it contains hydrocarbon chains on the polypeptide chain. HbA1c sensors are useful for monitoring blood glucose levels over the preceding 8–12 weeks. In addition, FcBA and Fc-modified boronic acids have been used for the detection of F− ions due to the selective binding of boronic acid to F− ions. F−-ion sensors may be useful alternatives to conventional ion-selective electrodes sensitive to F− ion. Furthermore, FcBA derivatives have been studied to construct lectin; steroids; nucleotides; salicylic acid; and bacteria sensors. One of the limitations of FcBA-based sensors comes from the fact that FcBA derivatives are added in sample solutions as reagents. FcBA derivatives should be immobilized on the surface of electrodes for developing reagentless sensors. PMID:25587421

  5. Electrochemical biosensors based on ferroceneboronic Acid and its derivatives: a review.

    PubMed

    Wang, Baozhen; Takahashi, Shigehiro; Du, Xiaoyan; Anzai, Jun-Ichi

    2014-09-01

    We review recent progress in the development of electrochemical biosensors based on ferroceneboronic acid (FcBA) and ferrocene (Fc)-modified boronic acids. These compounds can be used to construct electrochemical biosensors because they consist of a binding site (i.e., a boronic acid moiety) and an electrochemically active part (i.e., an Fc residue). By taking advantage of the unique properties of FcBA and its derivatives, electrochemical sensors sensitive to sugars, glycated hemoglobin (HbA1c), fluoride (F(-)) ions, and so forth have been widely studied. FcBA-based sugar sensors rely on the selective binding of FcBA to 1,2- or 1,3-diol residues of sugars through the formation of cyclic boronate ester bonds. The redox properties of FcBA-sugar adduct differ from those of free FcBA, which forms the basis of the electrochemical determination of sugars. Thus, non-enzymatic glucose sensors are now being actively studied using FcBA and Fc-modified boronic acids as redox markers. Using a similar principle, HbA1c can be detected by FcBA-based electrochemical systems because it contains hydrocarbon chains on the polypeptide chain. HbA1c sensors are useful for monitoring blood glucose levels over the preceding 8-12 weeks. In addition, FcBA and Fc-modified boronic acids have been used for the detection of F(-) ions due to the selective binding of boronic acid to F(-) ions. F(-)-ion sensors may be useful alternatives to conventional ion-selective electrodes sensitive to F(-) ion. Furthermore, FcBA derivatives have been studied to construct lectin; steroids; nucleotides; salicylic acid; and bacteria sensors. One of the limitations of FcBA-based sensors comes from the fact that FcBA derivatives are added in sample solutions as reagents. FcBA derivatives should be immobilized on the surface of electrodes for developing reagentless sensors. PMID:25587421

  6. 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.

  7. 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.

  8. Electrochemically induced annealing of stainless-steel surfaces.

    PubMed

    Burstein, G T; Hutchings, I M; Sasaki, K

    2000-10-19

    Modification of the surface properties of metals without affecting their bulk properties is of technological interest in demanding applications where surface stability and hardness are important. When austenitic stainless steel is heavily plastically deformed by grinding or rolling, a martensitic phase transformation occurs that causes significant changes in the bulk and surface mechanical properties of the alloy. This martensitic phase can also be generated in stainless-steel surfaces by cathodic charging, as a consequence of lattice strain generated by absorbed hydrogen. Heat treatment of the steel to temperatures of several hundred degrees can result in loss of the martensitic structure, but this alters the bulk properties of the alloy. Here we show that martensitic structures in stainless steel can be removed by appropriate electrochemical treatment in aqueous solutions at much lower temperature than conventional annealing treatments. This electrochemically induced annealing process allows the hardness of cold-worked stainless steels to be maintained, while eliminating the brittle martensitic phase from the surface. Using this approach, we are able to anneal the surface and near-surface regions of specimens that contain rolling-induced martensite throughout their bulk, as well as those containing surface martensite induced by grinding. Although the origin of the electrochemical annealing process still needs further clarification, we expect that this treatment will lead to further development in enhancing the surface properties of metals.

  9. Electrochemically induced annealing of stainless-steel surfaces

    NASA Astrophysics Data System (ADS)

    Burstein, G. T.; Hutchings, I. M.; Sasaki, K.

    2000-10-01

    Modification of the surface properties of metals without affecting their bulk properties is of technological interest in demanding applications where surface stability and hardness are important. When austenitic stainless steel is heavily plastically deformed by grinding or rolling, a martensitic phase transformation occurs that causes significant changes in the bulk and surface mechanical properties of the alloy. This martensitic phase can also be generated in stainless-steel surfaces by cathodic charging, as a consequence of lattice strain generated by absorbed hydrogen. Heat treatment of the steel to temperatures of several hundred degrees can result in loss of the martensitic structure, but this alters the bulk properties of the alloy. Here we show that martensitic structures in stainless steel can be removed by appropriate electrochemical treatment in aqueous solutions at much lower temperature than conventional annealing treatments. This electrochemically induced annealing process allows the hardness of cold-worked stainless steels to be maintained, while eliminating the brittle martensitic phase from the surface. Using this approach, we are able to anneal the surface and near-surface regions of specimens that contain rolling-induced martensite throughout their bulk, as well as those containing surface martensite induced by grinding. Although the origin of the electrochemical annealing process still needs further clarification, we expect that this treatment will lead to further development in enhancing the surface properties of metals.

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

    PubMed Central

    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. PMID:23575671

  11. 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.

  12. 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

  13. Mapping Electrochemical Heterogeneity at Iron Oxide Surfaces: A Local Electrochemical Impedance Study.

    PubMed

    Lucas, Marie; Boily, Jean-François

    2015-12-22

    Alternating current scanning electrochemical microscopy (AC-SECM) was used for the first time to map key electrochemical attributes of oriented hematite (α-Fe2O3) single crystal surfaces at the micron-scale. Localized electrochemical impedance spectra (LEIS) of the (001) and (012) faces provided insight into the spatial variations of local double layer capacitance (C(dl)) and charge transfer resistance (R(ad)). These parameters were extracted by LEIS measurements in the 0.4-8000 Hz range to probe the impedance response generated by the redistribution of water molecules and charge carriers (ions) under an applied AC. These were attributed to local variations in the local conductivity of the sample surfaces. Comparison with global EIS measurements on the same samples uncovered highly comparable frequency-resolved processes, that were broken down into contributions from the bulk hematite, the interface as well as the microelectrode/tip assembly. This work paves the way for new studies aimed at mapping electrochemical processes at the mesoscale on this environmentally and technologically important material.

  14. 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.

  15. Surface Morphology of Si(111) during Electrochemical Oxidation

    NASA Astrophysics Data System (ADS)

    Ando, A.; Miki, K.; Sakamoto, K.; Matsumoto, K.; Morita, Y.; Tokumoto, H.

    1997-03-01

    Topographical changes of hydrogen terminated Si(111) during electrochemical oxidation in a 0.2 M H_2SO4 aqueous solution have been investigated using atomic force microscopy (AFM). The hydrogen terminated surface with atomically flat terraces was prepared by dipping into a NH_4F aqueous solution. Electrochemical oxidation has been performed by a potentiostatic (constant potential) or a galvanostatic (constant current) method. AFM images show that the oxidation occured on the terraces and proceeded homogeneously. The surface became rough as the oxidation proceeded. However, step edges were still observed even after the charge of 50 mC/cm^2 was applied. Quantitative analysis of a relation between the charge and surface morphology will be discussed. the address below:

  16. 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.

  17. Electrochemical sensing and biosensing platform based on biomass-derived macroporous carbon materials.

    PubMed

    Wang, Li; Zhang, Qinying; Chen, Shuiliang; Xu, Fugang; Chen, Shouhui; Jia, Jianbo; Tan, Hongliang; Hou, Haoqing; Song, Yonghai

    2014-02-01

    A three-dimensional (3D) macroporous carbon (3D-KSCs) derived from kenaf stem (KS) is proposed as a novel supporting material for electrochemical sensing and a biosensing platform. A series of 3D-KSCs/inorganic nanocomposites such as Prussian blue (PB) nanoparticles (NPs)-carboxylic group-functionalized 3D-KSCs (PBNPs-3D-FKSCs), CuNiNPs-3D-KSCs, and CoNPs-3D-KSCs were prepared by a facile two-step route consisting of carbonization and subsequent chemical synthesis or one-step carbonization of KS-metal ion complex. The obtained 3D-KSCs/inorganic nanocomposites were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, scanning electron microscopy, and Fourier transform-infrared spectroscopy. A whole piece of 3D-KSCs/nanocomposites was used to prepare an integrated 3D-KSCs/nanocomposite electrode. Compared to the electrode modified by graphene, carbon nanotubes and their derivatives, which can form close-packed structure after assembled on electrode surface, the integrated 3D-KSCs/nanocomposite electrode shows a 3D honeycomb porous structure. Such structure provides a large specific surface area, effectively supports a large number of electro-active species, and greatly enhances the mass and electron transfer. The electrochemical behaviors and electrocatalytic performances of the integrated 3D-KSCs/inorganic nanocomposite electrode were evaluated by cyclic voltammetry and the amperometric method. The resulted PBNPs-3D-FKSCs, CuNiNPs-3D-KSCs, and CoNPs-3D-KSCs electrode show good electrocatalytic performances toward the reduction of H2O2, the oxidation of glucose and amino acid, respectively. Therefore, the low-cost, renewable, and environmentally friendly 3D-KSCs should be promising supporting materials for an electrochemical sensor and biosensor. PMID:24422469

  18. Application of electrochemical surface plasmon resonance spectroscopy for characterization of electrochemical DNA sensors.

    PubMed

    Salamifar, S Ehsan; Lai, Rebecca Y

    2014-10-01

    We report the use of electrochemical surface plasmon resonance spectroscopy (EC-SPR) in the characterization of electrochemical DNA sensors. Three DNA probes, including a stem-loop probe and two linear probes (LP), were used in this study. Among the three sensors, the 3xLP sensor, a new sensor design with three consecutive target recognition sites, showed the largest change in SPR signal upon hybridization to T-25, a 25-base target with overhang regions that do not bind to the 3xLP probe. A detection limit of 20nM was determined for T-25 using this sensor. Overall, this work has demonstrated the main advantage of EC-SPR, which is the ability to monitor both optical and electrochemical signals simultaneously, from sensor fabrication to target interrogation and sensor regeneration. It also alludes to the potential use of this hybrid technique to differentiate between non-specific binding and non-specific adsorption of non-complement targets onto the sensor surface.

  19. 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...

  20. 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...

  1. 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.

  2. Recent progress in electrochemical biosensors based on phenylboronic acid and derivatives.

    PubMed

    Anzai, Jun-Ichi

    2016-10-01

    This review provides an overview of recent progress made in the development of electrochemical biosensors based on phenylboronic acid (PBA) and its derivatives. PBAs are known to selectively bind 1,2- and 1,3-diols to form negatively charged boronate esters in neutral aqueous media and have been used to construct electrochemical glucose sensors because of this selective binding. PBA-modified metal and carbon electrodes have been widely studied as voltammetric and potentiometric glucose sensors. In some cases, ferroceneboronic acid or ferrocene-modified phenylboronic acids are used as sugar-selective redox compounds. Another option for sensors using PBA-modified electrodes is potentiometric detection, in which the changes in surface potential of the electrodes are detected as an output signal. An ion-sensitive field effect transistor (FET) has been used as a signal transducer in potentiometric sensors. Glycoproteins, such as glycated hemoglobin (HbA1c), avidin, and serum albumin can also be detected by PBA-modified electrodes because they contain hydrocarbon chains on the surface. HbA1c sensors are promising alternatives to enzyme-based glucose sensors for monitoring blood glucose levels over the preceding 2-3months. In addition, PBA-modified electrodes can be used to detect a variety of compounds including hydroxy acids and fluoride (F(-)) ions. PBA-based F(-) ion sensors may be useful if reagentless sensors can be developed.

  3. Recent progress in electrochemical biosensors based on phenylboronic acid and derivatives.

    PubMed

    Anzai, Jun-Ichi

    2016-10-01

    This review provides an overview of recent progress made in the development of electrochemical biosensors based on phenylboronic acid (PBA) and its derivatives. PBAs are known to selectively bind 1,2- and 1,3-diols to form negatively charged boronate esters in neutral aqueous media and have been used to construct electrochemical glucose sensors because of this selective binding. PBA-modified metal and carbon electrodes have been widely studied as voltammetric and potentiometric glucose sensors. In some cases, ferroceneboronic acid or ferrocene-modified phenylboronic acids are used as sugar-selective redox compounds. Another option for sensors using PBA-modified electrodes is potentiometric detection, in which the changes in surface potential of the electrodes are detected as an output signal. An ion-sensitive field effect transistor (FET) has been used as a signal transducer in potentiometric sensors. Glycoproteins, such as glycated hemoglobin (HbA1c), avidin, and serum albumin can also be detected by PBA-modified electrodes because they contain hydrocarbon chains on the surface. HbA1c sensors are promising alternatives to enzyme-based glucose sensors for monitoring blood glucose levels over the preceding 2-3months. In addition, PBA-modified electrodes can be used to detect a variety of compounds including hydroxy acids and fluoride (F(-)) ions. PBA-based F(-) ion sensors may be useful if reagentless sensors can be developed. PMID:27287174

  4. Electrochemical behavior of N-methyl-N'-carboxydecyl-4,4'-bipyridinium probed by surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Xu, Jian-Fang; Liu, Guo-Kun

    2013-10-01

    Interfacial structure determines the activity and selectivity of a sensor and plays important roles in interfacial electrochemistry, electroanalysis, biosensing, etc. In situ electrochemical Raman spectroscopy appears to be a powerful tool to probe the electrochemical interface and surface process by providing the molecular fingerprint information. Herein, the electrochemical behaviors of N-methyl-N'-carboxydecyl-4,4'-bipyridinium (derivatives of methyl viologens, MV2+) with different alkyl chain lengths (n = 2 and 10) on roughened Au electrodes were systematically investigated by the electrochemical surface-enhanced Raman spectroscopy (SERS). Three systems with different interfacial structures were constructed. One is to anchor the MV2+ molecules via esterification with the 2-mercaptoethanol molecule pre-assembled on the Au surface. The second system is similar to the first one but without esterification. The third system is the direct adsorption of MV2+ molecules on the bare roughened Au surfaces. The three systems gave different spectral response upon the change of the electrode potential. A drastically increased relative Raman intensity of 19a/8a modes of the MV2+ molecules was observed at negative potentials. The phenomenon is attributed to the formation of the reduced form of MV2+ molecules, which produces resonant Raman effect to enhanced the signal of 19a mode. The third system showed the highest electrochemical reduction activity towards the reduction of MV2+ molecules, followed by the first and second systems. The result indicates that the interfacial structure can sensitively influence electrochemical activity of the electrode.

  5. Surface morphology of nanotube formed Ti alloy by electrochemical methods.

    PubMed

    Kim, Sung-Hwan; Choe, Han-Cheol

    2014-11-01

    In order to investigate the surface morphology of nanotube formed Ti alloy by electrochemical methods, the Ti-6Al-4V alloys for dental implant were used in this study. Heat treatment was carried out at 800 degrees C for 1 hour and then water quenching in argon atmosphere, that will be have a specimen name of 800 WQ. The formation of nanotube structure was conducted by electrochemical method on Ti-6Al-4V alloy in mixed electrolytes at 30 V for 1 hour. Microstructure of β phases showed dot-like structures at non-treated Ti-6Al-4V alloy, and needle-like in equiaxed structure from treated the alloy at 800 WQ. In non-treated Ti-6Al-4V alloy case, nanotubes only exhibited at α phase region with dissolved V-oxide area of β phase. However, in the case of 800 WQ, nanotubes of Ti-6Al-4V alloy exhibited at both α and βphase region. Electrochemical corrosion studies showed that the nanotubular alloy of 800 WQ possesses slightly higher corrosion resistance than that of non-treated nanotubular alloy. PMID:25958530

  6. 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.

  7. Flavin Derivatives with Tailored Redox Properties: Synthesis, Characterization, and Electrochemical Behavior.

    PubMed

    Kormányos, Attila; Hossain, Mohammad S; Ghadimkhani, Ghazaleh; Johnson, Joe J; Janáky, Csaba; de Tacconi, Norma R; Foss, Frank W; Paz, Yaron; Rajeshwar, Krishnan

    2016-06-27

    This study establishes structure-property relationships for four synthetic flavin molecules as bioinspired redox mediators in electro- and photocatalysis applications. The studied flavin compounds were disubstituted with polar substituents at the N1 and N3 positions (alloxazine) or at the N3 and N10 positions (isoalloxazines). The electrochemical behavior of one such synthetic flavin analogue was examined in detail in aqueous solutions of varying pH in the range from 1 to 10. Cyclic voltammetry, used in conjunction with hydrodynamic (rotating disk electrode) voltammetry, showed quasi-reversible behavior consistent with freely diffusing molecules and an overall global 2e(-) , 2H(+) proton-coupled electron transfer scheme. UV/Vis spectroelectrochemical data was also employed to study the pH-dependent electrochemical behavior of this derivative. Substituent effects on the redox behavior were compared and contrasted for all the four compounds, and visualized within a scatter plot framework to afford comparison with prior knowledge on mostly natural flavins in aqueous media. Finally, a preliminary assessment of one of the synthetic flavins was performed of its electrocatalytic activity toward dioxygen reduction as a prelude to further (quantitative) studies of both freely diffusing and tethered molecules on various electrode surfaces. PMID:27243969

  8. 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.

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

    NASA Astrophysics Data System (ADS)

    Pollard, Travis P.; Beck, Thomas L.

    2014-11-01

    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.

  10. Transient Electrochemical Surface-Enhanced Raman Spectroscopy: A Millisecond Time-Resolved Study of an Electrochemical Redox Process.

    PubMed

    Zong, Cheng; Chen, Chan-Juan; Zhang, Meng; Wu, De-Yin; Ren, Bin

    2015-09-16

    The pursuit of techniques with a high time resolution together with molecular signature information at the electrochemical interfaces has never stopped in order to explicitly monitor and understand the dynamic electrochemical processes. Here, we developed a transient electrochemical surface-enhanced Raman spectroscopy (TEC-SERS) to monitor the structural evolution of surface species at a time resolution that equals the transient electrochemical methods (e.g., cyclic voltammetry and chronoamperometry), so that the Raman signal with the molecular signature information and the electrochemical current signal can be precisely correlated. The technique was employed to study the redox process of nile blue on Ag surfaces. We revealed an interesting two-rate constant process and a peculiar increase of the absolute intensity during the reduction of nile blue on the Ag surface, which both related to the dissociation of nile blue aggregates and the follow-up reduction. Therefore, we were able to uncover the processes that are impossible to observe by conventional steady state SERS methods. The ability to provide a time resolution shorter than the charging time of the double layer capacitance with molecular fingerprint information has unprecedented significance for investigation of both reversible and irreversible electrochemical processes.

  11. 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.

  12. Electrochemical accumulation of visible gold on pyrite and arsenopyrite surfaces

    NASA Astrophysics Data System (ADS)

    Möller, P.; Kersten, G.

    1994-09-01

    In galvanic cell arrangements gold is electrochemically deposited on semiconducting sulfide minerals (pyrite, arsenopyrite, chalcopyrite) from aerated as well as H2S-saturated, gold-bearing 1 M KCl solutions. Observed cell potential differences of about 0.4 0.6 V in setups with one sulfide in aerated (cathode) and the other in H2S-saturated (anode) solutions are comparable with known “self-potentials” of natural sulfide ore bodies. Gold preferentially accumulates on the cathode, i.e. under oxidizing conditions. Linked sulfides of variable composition in the same environment, either oxidizing or reducing, yield potential differences up to 20 mV. Such assemblages simulate conditions typically occurring at surfaces of chemically inhomogeneous single crystals (e.g. zonation). Depending on chemical composition, sulfide minerals show either n- or p-type conductivity. Visible gold is preferentially accumulated on individual domains of sulfide surfaces that act as cathodes, i.e. p-type conductors in n-p junctions. The experimental results are discussed in view of electrochemical accumulation of visible gold on sulfides in nature. Arsenic is the most important element in establishing p-type conductivity of pyrite and arsenopyrite. This feature may explain why As is such a powerful pathfinder in gold exploration.

  13. 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

    2016-04-01

    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. PMID:26928030

  14. Surface effects and electrochemical cell capacitance in desorption electrospray ionization.

    PubMed

    Volný, Michael; Venter, Andre; Smith, Scott A; Pazzi, Marco; Cooks, R Graham

    2008-04-01

    Time resolved measurements show that during a desorption electrospray ionization (DESI) experiment, the current initially rises sharply, followed by an exponential decrease to a relatively steady current. When the high voltage on the spray emitter is switched off, the current drops to negative values, suggesting that the direction of current flow in the equivalent DESI circuit is reversed. These data demonstrate that the DESI source behaves as a dc capacitor and that the addition of a surface between the sprayer and the counter electrode in DESI introduces a new electrically active element into the system. The charging and discharging behavior was observed using different surfaces and it could be seen both by making current measurements on a plate at the entrance to the mass spectrometer as well as by measuring ion current in the linear ion trap within the vacuum system of the mass spectrometer. The magnitude of the steady state current obtained without analyte present on the surface is different for different surface materials, and different capacitor time constants of the equivalent RC circuits were calculated for different DESI surfaces. The PTFE surface has by far the greatest time constant and is also able to produce the highest DESI currents. Surface properties play a crucial role in charge transfer during DESI in addition to the effects of the chemical properties of the analyte. It is suggested that surface energy (wettability) is an important factor controlling droplet behavior on the surface. The experimental data are correlated with critical surface tension values of different materials. It is proposed, based on the results presented, that super-hydrophobic materials with extremely high contact angles have the potential to be excellent DESI substrates. It is also demonstrated, using the example of the neurotransmitter dopamine, that the surface charge that develops during a DESI-MS experiment can cause electrochemical oxidation of the analyte. PMID

  15. Surface effects and electrochemical cell capacitance in desorption electrospray ionization.

    PubMed

    Volný, Michael; Venter, Andre; Smith, Scott A; Pazzi, Marco; Cooks, R Graham

    2008-04-01

    Time resolved measurements show that during a desorption electrospray ionization (DESI) experiment, the current initially rises sharply, followed by an exponential decrease to a relatively steady current. When the high voltage on the spray emitter is switched off, the current drops to negative values, suggesting that the direction of current flow in the equivalent DESI circuit is reversed. These data demonstrate that the DESI source behaves as a dc capacitor and that the addition of a surface between the sprayer and the counter electrode in DESI introduces a new electrically active element into the system. The charging and discharging behavior was observed using different surfaces and it could be seen both by making current measurements on a plate at the entrance to the mass spectrometer as well as by measuring ion current in the linear ion trap within the vacuum system of the mass spectrometer. The magnitude of the steady state current obtained without analyte present on the surface is different for different surface materials, and different capacitor time constants of the equivalent RC circuits were calculated for different DESI surfaces. The PTFE surface has by far the greatest time constant and is also able to produce the highest DESI currents. Surface properties play a crucial role in charge transfer during DESI in addition to the effects of the chemical properties of the analyte. It is suggested that surface energy (wettability) is an important factor controlling droplet behavior on the surface. The experimental data are correlated with critical surface tension values of different materials. It is proposed, based on the results presented, that super-hydrophobic materials with extremely high contact angles have the potential to be excellent DESI substrates. It is also demonstrated, using the example of the neurotransmitter dopamine, that the surface charge that develops during a DESI-MS experiment can cause electrochemical oxidation of the analyte.

  16. 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.

  17. 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.

  18. 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.

  19. Electrochemical chlorine evolution at rutile oxide (110) surfaces.

    PubMed

    Hansen, Heine A; Man, Isabela C; Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas; Rossmeisl, Jan

    2010-01-01

    Based on density functional theory (DFT) calculations we study the electrochemical chlorine evolution reaction on rutile (110) oxide surfaces. First we construct the Pourbaix surface diagram for IrO(2) and RuO(2), and from this we find the chlorine evolution reaction intermediates and identify the lowest overpotential at which all elementary reaction steps in the chlorine evolution reaction are downhill in free energy. This condition is then used as a measure for catalytic activity. Linear scaling relations between the binding energies of the intermediates and the oxygen binding energies at cus-sites are established for MO(2) (M being Ir, Ru, Pt, Ti). The linear relations form the basis for constructing a generalized surface phase diagram where two parameters, the potential and the binding energy of oxygen, are needed to determine the surface composition. We calculate the catalytic activity as function of the oxygen binding energy, giving rise to a Sabatier volcano. By combining the surface phase diagram and the volcano describing the catalytic activity, we find that the reaction mechanism differs depending on catalyst material. The flexibility in reaction path means that the chlorine evolution activity is high for a wide range of oxygen binding energies. We find that the required overpotential for chlorine evolution is lower than the overpotential necessary for oxygen evolution. PMID:20024470

  20. Poly(3-phenylthiophene) derivatives as active materials for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Eissa, Mona M.

    Poly(3-(4-methylsulfonylphenyl)thiophenes) (PMSPT), (3-(4-cyanophenyl)-thiophene) (PCNPT), (3-(3,4-difluorophenyl)thiophene) (MPFPT), (3-(3,5difluorophenyl)thiophene) (MMFPT), and (3-(3-fluorophenyl)thiophene) (MFPT) polymers were prepared and electrochemically characterized in various organic electrolytes. The morphologies and electrochemical performance of the films were shown to depend on both the growth and cycling electrolytes. Constant current multicycle tests were performed on single cell devices using the type III capacitor configuration at high voltage (2.8-2.9 V) employing MPFPT, PCNPT, PMSPT and PFPT polymers. Energy and power densities of up to 50 Wh/kg and 5 kW/kg were achieved and excellent stabilities (up to 1200 n-doping/dedoping cycles) were demonstrated. Industrial practicum. The industrial practicum report on "Chemical Vapor Deposition of High Performance Polymeric Thin Films for Advanced Interconnect Applications" determined the copolymerization and characterization of four novel copolymers of Parylene-N by a CVD process at low temperature. These copolymers retain the advantages of the CVD process and also modify the properties of the Parylene homopolymer significantly such as lowering the dielectric constant from 2.65 to ˜2.0, increasing the thermal stability and enhancing the adhesion. Apprenticeship practicum. The study on "Synthesis, Characterization, and Catalytic Activity of The Zeolite Encapsulated Ruthenium hexadeca-fluorophthalocyanine Complexes" determined the catalytic activity of this fluorinated ruthenium phthalocyanine which was encapsulated in zeolite NaX during crystallization. Both the free complex RuFsb{16}Pc and the encapsulated (RuFsb{16}Pc-NaX) were found to be effective catalysts for the oxidation of cyclohexane with high efficiency and stability.

  1. Surface-enhanced Raman spectroscopy of amino acids adsorbed on an electrochemically prepared silver surface

    NASA Astrophysics Data System (ADS)

    Stewart, S.; Fredericks, P. M.

    1999-07-01

    An electrochemically roughened silver surface, in conjunction with a Raman microprobe spectrometer, was used to obtain SER spectra of a suite of 19 L-amino acids. The spectra obtained were very different from previously reported SER spectra obtained from silver hydrosols of amino acids. Analysis of the spectra showed that adsorption of all amino acids was via the ionised carboxylate group, and that the side chain of most of the molecules was also in close proximity to the surface. The spectra also indicated that, in contrast, the amine terminus was protonated and relatively far from the surface. Sulfur-containing amino acids also interacted with the silver surface through their sulfur atoms.

  2. Synthesis and Characterization of Self-Assembled Monolayers Derived Electrochemically from o-Functionalized Alkyl Thiosulfates

    NASA Astrophysics Data System (ADS)

    Labukas, Joseph Paul

    The ability to control the placement of molecules onto substrates is an important challenge for advancing the development of sensor technologies. Although self-assembled monolayers (SAMs) of alkyl thiolates on gold have been rigorously studied, achieving regiochemical control in this system is more challenging. Using alkyl thiosulfates, SAM formation can be directed electrochemically, thereby alleviating potential difficulties associated with approaches that use thiol chemistry. The first challenge of this research was to determine which u-functionalities are compatible with the electrosynthesis of monolayers from alkyl thiosulfates. The elemental compositions of methyl-, perfluoroalkyl-, carboxylic acid-, amide-, and methyl ester-terminated SAMs derived from alkyl thiosulfates were similar to those measured for analogous SAMs derived from thiols. In contrast, x-ray photoelectron spectroscopy (XPS) revealed that by-products of the electrosynthesis react with the terminal functionality of the hydroxyl- and vinyl-terminated SAMs. Mixed monolayers formed from solutions containing two-different alkyl thiosulfates allowed enhanced flexibility in controlling the surface properties of electrodes. The surface composition of these two-component systems was determined kinetically and was therefore linearly related to the solution composition from which they were derived. To demonstrate the selectivity of the electrosynthesis, different monolayers were directed onto individually addressable electrodes in arrays. Initially, four different monolayers were placed on four adjacent electrodes on a single substrate. To gain insight into the applicability of this technology at the microscale, an array containing three microelectrodes was functionalized sequentially with a different monolayer on each electrode. Using XPS and measurements of wettability, the presence of u-functionalized SAMs was detected only on electrodes to which they were directed.

  3. 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

  4. Structural characterization and electrochemical properties of novel salicylidene phosphonate derivatives

    NASA Astrophysics Data System (ADS)

    Dolaz, Mustafa; McKee, Vickie; Köse, Muhammet; Gölcü, Ayşegül; Tümer, Mehmet

    2010-09-01

    In this study, three novel salicylidene phosphonate ligands, diethyl (4-{[(1 E)-(2-hydroxyphenyl)methylidene]amino}benzyl)phosphonate (HL 1), diethyl (4-{[(1 E)-(2-hydroxy-3-methoxyphenyl)methylidene]amino}benzyl)phosphonate (HL 2) and diethyl (4-{[(1 E)-(2,4-dihydroxyphenyl)methylidene]amino}benzyl)phosphonate (HL 3) were synthesized and characterized by the analytical and spectroscopic techniques. We obtained their single crystals from the ethanolic solution. There are intramolecular phenol-imine hydrogen bonds in all three compounds between O1 and N1 atoms. The ligand HL 3 contains a second phenol group and this is makes an intermolecular hydrogen bond with the phosphine oxide of a neighbouring molecule O2-O3 (under symmetry operation - x, 0.5 + y, 0.5 - z). In order to investigate the redox behaviours of the salicylidene phosphonate ligands (HL 1-HL 3), we were studied electrochemical properties of the ligands at the different pH and scan rates.

  5. 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

  6. 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.

  7. Hydrothermal synthesis of ordered mesoporous carbons from a biomass-derived precursor for electrochemical capacitors.

    PubMed

    Feng, Shanshan; Li, Wei; Wang, Jinxiu; Song, Yanfang; Elzatahry, Ahmed A; Xia, Yongyao; Zhao, Dongyuan

    2014-12-21

    Here, we report the reproducible synthesis of highly ordered mesoporous carbons (OMCs) with a 2D hexagonal mesostructure via a facile hydrothermal method employing β-cyclodextrin as a renewable and environmentally-friendly carbon precursor, which gives the OMCs a high surface area and micropore surface areas, as well as an oxygenated surface. As a supercapacitor electrode, these OMCs exhibit a high specific capacitance and a high electrochemical stability.

  8. 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.

  9. Urethane tetrathiafulvalene derivatives: synthesis, self-assembly and electrochemical properities

    PubMed Central

    Sun, Xiang; Lai, Guoqiao; Li, Zhifang; Ma, Yuwen; Yuan, Xiao; Shen, Yongjia

    2015-01-01

    Summary This paper reports the self-assembly of two new tetrathiafulvalene (TTF) derivatives that contain one or two urethane groups. The formation of nanoribbons was evidenced by scanning electron microscopy (SEM) and X-ray diffraction (XRD), which showed that the self-assembly ability of T 1 was better than that of T 2. The results revealed that more urethane groups in a molecule did not necessarily instigate self-assembly. UV–vis and FTIR spectra were measured to explore noncovalent interactions. The driving forces for self-assembly of TTF derivatives were mainly hydrogen bond interactions and π–π stacking interactions. The electronic conductivity of the T 1 and T 2 films was tested by a four-probe method. PMID:26734083

  10. Impact of Surface Chemistry on Nanoparticle-Electrode Interactions in the Electrochemical Detection of Nanoparticle Collisions.

    PubMed

    Chen, Chang-Hui; Ravenhill, Emma R; Momotenko, Dmitry; Kim, Yang-Rae; Lai, Stanley C S; Unwin, Patrick R

    2015-11-01

    The electrochemical detection of a single nanoparticle (NP) at a support electrode can provide key information on surface chemistry and fundamental electron transfer (ET) properties at the nanoscale. This study employs scanning electrochemical cell microscopy (SECCM) as a fluidic device to both deliver individual citrate-capped gold nanoparticles (AuNPs) and study the interactions between them and a range of alkanethiol-modified Au electrodes with different terminal groups, namely, -COOH, -OH, and -CH3. Single NP collisions were detected through the AuNP-mediated ET reaction of Fe(CN)6(4-/3-) in aqueous solution. The collision frequency, residence time, and current-time characteristics of AuNPs are greatly affected by the terminal groups of the alkanethiol. Methods to determine these parameters, including the effect of the instrument response function, and derive ET kinetics are outlined. To further understand the interactions of AuNPs with these surfaces, atomic force microscopy (AFM) force measurements were performed using citrate-modified Au-coated AFM tips and the same alkanethiol-modified Au substrates in aqueous solution at the same potential bias as for the AuNP collision experiments. Force curves on OH-terminated surfaces showed no repulsion and negligible adhesion force. In contrast, a clear repulsion (on approach) was seen for COOH-terminated surface and adhesion forces (on retract) were observed for both COOH- and CH3-terminated surfaces. These interactions help to explain the residence times and collision frequencies in AuNP collisions. More generally, as the interfacial properties probed by AFM appear to be amplified in NP collision experiments, and new features also become evident, it is suggested that such experiments provide a new means of probing surface chemistry at the nanoscale.

  11. 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.

  12. 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.

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

    PubMed

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

    2011-01-01

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

  14. Electrochemical Examination of the Structure of Thin Hydrogel Layers Anchored to Regular and Microelectrode Surfaces.

    PubMed

    Kaniewska, Klaudia; Karbarz, Marcin; Ziach, Krzysztof; Siennicka, Alicja; Stojek, Zbigniew; Hyk, Wojciech

    2016-09-01

    For the examination of hydrogel structure, thin layers of thermoresponsive gels based on poly(N-isopropylacrylamide) (pNIPA) and copolymer poly(N-isopropylacrylamide-co-sodium acrylate) (p(NIPA-co-AS)) were successfully anchored to microelectrode and regular electrode surfaces using the electrochemically induced free radical polymerization. The obtained layers were stable and covered the entire surface of the electrodes. Electroactive probes 1,1'-ferrocenedimethanol (Fc(CH2OH)2) and synthesized derivatives of ferrocene modified with polyethylene glycol units (Fc-PEGn) of various length (n = 4, 9, 75, and 135) were employed for studying the volume phase transition of the thin hydrogel layers and for the determination of their structural parameters. The quantitative information on the structural parameters of the hydrogel layers was derived from the obstruction model for diffusion using the voltammetrically determined diffusion coefficients for the model redox probe Fc(CH2OH)2. An approach to the determination of the effective radii of the gel openings (channels) for pNIPA and p(NIPA-co-AS) microlayers was developed. The obtained results were matched with the experimental results and allowed derivation of quantitative conclusions. The voltammograms obtained with modified electrodes in solutions containing Fc-PEG4, Fc-PEG9, and Fc-PEG75 were well defined and of appropriate height. However, the voltammograms recorded for Fc-PEG135, the hydrodynamic radius of which exceeded the size of the gel channels, were at the baseline level. PMID:27518807

  15. Electrochemical Examination of the Structure of Thin Hydrogel Layers Anchored to Regular and Microelectrode Surfaces.

    PubMed

    Kaniewska, Klaudia; Karbarz, Marcin; Ziach, Krzysztof; Siennicka, Alicja; Stojek, Zbigniew; Hyk, Wojciech

    2016-09-01

    For the examination of hydrogel structure, thin layers of thermoresponsive gels based on poly(N-isopropylacrylamide) (pNIPA) and copolymer poly(N-isopropylacrylamide-co-sodium acrylate) (p(NIPA-co-AS)) were successfully anchored to microelectrode and regular electrode surfaces using the electrochemically induced free radical polymerization. The obtained layers were stable and covered the entire surface of the electrodes. Electroactive probes 1,1'-ferrocenedimethanol (Fc(CH2OH)2) and synthesized derivatives of ferrocene modified with polyethylene glycol units (Fc-PEGn) of various length (n = 4, 9, 75, and 135) were employed for studying the volume phase transition of the thin hydrogel layers and for the determination of their structural parameters. The quantitative information on the structural parameters of the hydrogel layers was derived from the obstruction model for diffusion using the voltammetrically determined diffusion coefficients for the model redox probe Fc(CH2OH)2. An approach to the determination of the effective radii of the gel openings (channels) for pNIPA and p(NIPA-co-AS) microlayers was developed. The obtained results were matched with the experimental results and allowed derivation of quantitative conclusions. The voltammograms obtained with modified electrodes in solutions containing Fc-PEG4, Fc-PEG9, and Fc-PEG75 were well defined and of appropriate height. However, the voltammograms recorded for Fc-PEG135, the hydrodynamic radius of which exceeded the size of the gel channels, were at the baseline level.

  16. Palladium nanoparticles supported on nitrogen-doped HOPG: a surface science and electrochemical study.

    PubMed

    Favaro, Marco; Agnoli, Stefano; Perini, Lorenzo; Durante, Christian; Gennaro, Armando; Granozzi, Gaetano

    2013-02-28

    We have investigated by photoemission spectroscopy and scanning tunnelling microscopy what are the chemical and structural changes induced by nitrogen ion implantation (500 eV) on highly oriented pyrolytic graphite and how the defects induced by this process modify the growth and thermal stability of palladium nanoparticles, deposited in situ by physical vapour deposition. Since nitrogen derived defects are mostly buried below the surface, they are not accessible for a chemical interaction with metal nanoparticles; however, the amorphization induced by the ion beam in the outermost layers of the substrate beneficially affects the metal morphology, limiting the size of the nanoparticles and improving their thermal stability. The supported nanoparticles have been tested towards the oxygen reduction reaction indicating that the electrochemical activity does not depend significantly on the ion implantation, but mostly on the amount of palladium.

  17. Dominant Role of Molybdenum in the Electrochemical Deposition of Biological Macromolecules on Metallic Surfaces

    PubMed Central

    2014-01-01

    The corrosion of CoCrMo, an alloy frequently used in orthopedic implants, was studied with an electrochemical quartz crystal microbalance (QCM) in three physiologically relevant solutions. Mass changes were measured during potentiodynamic tests, showing material deposition in protein solutions at potential levels that caused mass loss when the proteins were not present. X-ray photoelectron spectroscopy (XPS) data indicated that the deposited material was primarily organic and therefore was most likely derived from proteins in the electrolyte. Material deposition consistently occurred at a critical potential and was not dependent on the current density or total charge released into solution. Corrosion studies on pure Co, Cr, and Mo in protein solutions found material deposition only on Mo. We hypothesize that organic deposition results from the interaction of Mo(VI) with proteins in the surrounding solution. The organic layer is reminiscent of tribochemical reaction layers that form on the surface of CoCrMo hip bearings, suggesting that these types of layers can be formed by purely electrochemical means. PMID:23550942

  18. Electrochemical lithiation-induced polymorphism of anthraquinone derivatives observed by operando X-ray diffraction.

    PubMed

    Silberstein, Katharine E; Pastore, James P; Zhou, Weidong; Potash, Rebecca A; Hernández-Burgos, Kenneth; Lobkovsky, Emil B; Abruña, Héctor D

    2015-11-01

    The use of organic molecules represents a very attractive and promising alternative for electrical energy storage applications. Quinones, in general, and anthraquinones, in particular, are especially attractive due to their ability to reversibly exchange multiple electrons per formula unit. When used as the active electrode material in a real lithium-ion battery (LIB), crystalline anthraquinone powders reversibly change crystal packing as a function of state-of-charge (redox state), with well-defined voltage plateaus appearing concomitantly with new phases. Operando powder X-ray diffraction (XRD) is a powerful method for screening the structural stability of organic cathode candidates and for understanding electrochemically-induced structural transformations within organic molecular crystals. Herein we explore the electrochemical lithiation-induced polymorphism of anthraquinone (AQ) and three related derivatives. We believe that this analysis can serve as a model for studying organic charge storage within crystalline small-molecule candidates. PMID:26427626

  19. Corrosion resistance properties of superhydrophobic copper surfaces fabricated by one-step electrochemical modification process

    NASA Astrophysics Data System (ADS)

    Huang, Ying; Sarkar, D. K.; Gallant, Danick; Chen, X.-Grant

    2013-10-01

    Superhydrophobic copper surfaces have been prepared by a one-step electrochemical modification process in an ethanolic stearic acid solution. In this work, the corrosion properties of hydrophobic copper surface and superhydrophobic copper surfaces were analyzed by means of electrochemical analyses and compared with that of as-received bare copper substrate. The decrease of corrosion current density (icorr) as well as the increase of polarization resistance (Rp) obtained from potentiodynamic polarization curves revealed that the superhydrophobic film on the copper surfaces improved the corrosion resistance performance of the copper substrate.

  20. 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.

  1. Surface Morphologies of Electrochemically Prepared Materials Simulated by Reaction-diffusion Models

    NASA Astrophysics Data System (ADS)

    Boscheto, Emerson Paulinho; Lopes, Mauro Chierici

    2005-07-01

    The emergence of spatial patterns in electrochemically formed materials opens the possibility to exploit nonlinear behavior to devise a technique for electrochemical preparation of materials with unique properties arising from their spatial organization. In this paper, we discuss the mechanism of Turing pattern formation on the electrode surface. We propose a modification of the Brusselator model, which includes an inhomogeneous influx of the autocatalytic specie. Several kinds of patterns were simulated.

  2. Surface patterning of polyacrylamide gel using scanning electrochemical cell microscopy (SECCM).

    PubMed

    Oseland, Elizabeth E; Ayres, Zoë J; Basile, Andrew; Haddleton, David M; Wilson, Paul; Unwin, Patrick R

    2016-08-01

    Scanning electrochemical cell microscopy is introduced as a new tool for the synthesis and deposition of polymers on SAM-functionalised Au surfaces. The deposition of poly(N-hydroxyethyl acrylamide) is shown to be enhanced through the electrochemical generation of activating Cu(i)Cl/Me6TREN catalyst. Initiation of the polymerisation reaction is most likely due to in situ generation of reactive oxygen species following oxygen reduction.

  3. 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. PMID:27082127

  4. 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.

  5. 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.

  6. Electrochemical Behavior of Quinoxalin-2-one Derivatives at Mercury Electrodes and Its Analytical Use

    PubMed Central

    Zimpl, Milan; Skopalova, Jana; Jirovsky, David; Bartak, Petr; Navratil, Tomas; Sedonikova, Jana; Kotoucek, Milan

    2012-01-01

    Derivatives of quinoxalin-2-one are interesting compounds with potential pharmacological activity. From this point of view, understanding of their electrochemical behavior is of great importance. In the present paper, a mechanism of electrochemical reduction of quinoxalin-2-one derivatives at mercury dropping electrode was proposed. Pyrazine ring was found to be the main electroactive center undergoing a pH-dependent two-electron reduction process. The molecule protonization of nitrogen in the position 4 precedes the electron acceptance forming a semiquinone radical intermediate which is relatively stable in acidic solutions. Its further reduction is manifested by separated current signal. A positive mesomeric effect of the nonprotonized amino group in the position 7 of the derivative III accelerates the semiquinone reduction yielding a single current wave. The suggested reaction mechanism was verified by means of direct current polarography, differential pulse, cyclic and elimination voltammetry, and coulometry with subsequent GC/MS analysis. The understanding of the mechanism was applied in developing of analytical method for the determination of the studied compounds. PMID:22666117

  7. 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.

  8. 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.

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

    DOE PAGESBeta

    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 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

  10. Au nanostructured surfaces for electrochemical and localized surface plasmon resonance-based monitoring of α-synuclein-small molecule interactions.

    PubMed

    Cheng, Xin R; Wallace, Gregory Q; Lagugné-Labarthet, François; Kerman, Kagan

    2015-02-25

    In this proof-of-concept study, the fabrication of novel Au nanostructured indium tin oxide (Au-ITO) surfaces is described for the development of a dual-detection platform with electrochemical and localized surface plasmon resonance (LSPR)-based biosensing capabilities. Nanosphere lithography (NSL) was applied to fabricate Au-ITO surfaces. Oligomers of α-synuclein (αS) were covalently immobilized to determine the electrochemical and LSPR characteristics of the protein. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were performed using the redox probe [Fe(CN)6](3-/4-) to detect the binding of Cu(II) ions and (-)-epigallocatechin-3-gallate (EGCG) to αS on the Au-ITO surface. Electrochemical and LSPR data were complemented by Thioflavin-T (ThT) fluorescence, surface plasmon resonance imaging (SPRi), and transmission electron microscopy (TEM) studies. EGCG was shown to induce the formation of amorphous aggregates that decreased the electrochemical signals. However, the binding of EGCG with αS increased the LSPR absorption band with a bathochromic shift of 10-15 nm. The binding of Cu(II) to αS enhanced the DPV peak current intensity. NSL fabricated Au-ITO surfaces provide a promising dual-detection platform to monitor the interaction of small molecules with proteins using electrochemistry and LSPR.

  11. 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.

  12. Surface electrochemical properties of red mud (bauxite residue): zeta potential and surface charge density.

    PubMed

    Liu, Yanju; Naidu, Ravendra; Ming, Hui

    2013-03-15

    The surface electrochemical properties of red mud (bauxite residue) from different alumina refineries in Australia and China were studied by electrophoresis and measuring surface charge density obtained from acid/base potentiometric titrations. The electrophoretic properties were measured from zeta potentials obtained in the presence of 0.01 and 0.001 M KNO(3) over a wide pH range (3.5-10) by titration. The isoelectric point (IEP) values were found to vary from 6.35 to 8.70 for the red mud samples. Further investigation into the surface charge density of one sample (RRM) by acid/base potentiometric titration showed similar results for pH(PZC) with pH(IEP) obtained from electrokinetic measurements. The pH(IEP) determined from zeta potential measurements can be used as a characteristic property of red mud. The minerals contained in red mud contributed to the different values of pH(IEP) of samples obtained from different refineries. Different relationships of pH(IEP) with Al/Fe and Al/Si ratios (molar basis) were also found for different red mud samples. PMID:23270758

  13. 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.

  14. Electrochemical assembling of methionine-gold nanoparticles and catalysis on the surface of glassy carbon electrode

    NASA Astrophysics Data System (ADS)

    Song, Y. Z.; Wang, J. H.; Zhang, X. M.; Cao, W.; Ge, A.; Zhou, L.

    2014-12-01

    In this paper cyclic voltammetry was used for the synthesis of linear array spherical gold nanoparticles on the surface of glassy carbon electrode using methionine as a stable reagent. The methionine-gold nanoparticles on the surface of glassy electrode were obtained. The methionine-gold nanoparticles were characterized by cyclic voltammetry, scanning electron microscopy, energy dispersive spectrometry and powder X-ray diffraction. Electrochemical behavior of methionine at methionine-gold nanoparticle modified electrode was investigated. It was demonstrated that the methionine-gold nanoparticles can catalyze electrochemical transformations of methionine.

  15. Corrosion Behavior of Surface-Treated Implant Ti-6Al-4V by Electrochemical Polarization and Impedance Studies

    NASA Astrophysics Data System (ADS)

    Paul, Subir; Yadav, Kasturi

    2011-04-01

    Implant materials for orthopedic and heart surgical services demand a better corrosion resistance material than the presently used titanium alloys, where protective oxide layer breaks down on a prolonged stay in aqueous physiological human body, giving rise to localized corrosion of pitting, crevice, and fretting corrosion. A few surface treatments on Ti alloy, in the form of anodization, passivation, and thermal oxidation, followed by soaking in Hank solution have been found to be very effective in bringing down the corrosion rate as well as producing high corrosion resistance surface film as reflected from electrochemical polarization, cyclic polarization, and Electrochemical Impedance Spectroscopy (EIS) studies. The XRD study revealed the presence of various types of oxides along with anatase and rutile on the surface, giving rise to high corrosion resistance film. While surface treatment of passivation and thermal oxidation could reduce the corrosion rate by 1/5th, anodization in 0.3 M phosphoric acid at 16 V versus stainless steel cathode drastically brought down the corrosion rate by less than ten times. The mechanism of corrosion behavior and formation of different surface films is better understood from the determination of EIS parameters derived from the best-fit equivalent circuit.

  16. 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.

  17. A comparison of electrochemical and gas-phase decomposition of methanol on platinum surfaces

    SciTech Connect

    Franaszczuk, K.; Herrero, E.; Zelenay, P.

    1992-10-15

    By using electrochemical and ultrahigh-vacuum (UHV) techniques, combined with an isotope substitution method, it is found that the mechanism of methanol decomposition on platinum in the electrochemical environment is different than that in the UHV. In the UHV, the first step in the decomposition process is the scission of an O-H bond to yield a methoxy intermediate, whereas in the electrochemical environment, the first step is the scission of a C-H bond. The difference in the decomposition mechanism is discussed in terms of differences in the local electric field at the surface and in terms of methanol hydrophobic/hydrophilic interactions in solution. The latter affect methanol-water near-surface conformation and predetermine the destiny of the individual methanolic bonds in the catalytic splitting. 51 refs., 11 figs., 4 tabs.

  18. 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.

  19. 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. PMID:24039010

  20. 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

    2015-10-01

    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.

  1. 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

    2015-10-01

    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. PMID:26307480

  2. Vibrational and electronic characterization of ethynyl derivatives grafted onto hydrogenated Si(111) surfaces.

    PubMed

    Yang, F; Hunger, R; Roodenko, K; Hinrichs, K; Rademann, K; Rappich, J

    2009-08-18

    Covalent grafting of ethynyl derivatives (-C triple bond C-H, -C triple bond C-CH3, -C triple bond C-aryl) onto H-terminated Si(111) surfaces was performed by a one-step anodic treatment in Grignard electrolytes. The electrochemical grafting of such ethynyl derivatives, which tends to form ultrathin polymeric layers, can be controlled by the current and charge flow passing through the Si electrode. The prepared ultrathin layers cover the Si surface and had a thickness up to 20 nm, as investigated by the scanning electron microscopy (SEM) technique. Exchanging Cl for Br in the ethynyl Grignard reagent leads to very thin layers, even under the same electrochemical conditions. However, for all ethynyl derivatives, high-resolution synchrotron X-ray photoelectron spectroscopy (SXPS) investigations reveal the incorporation of halogen atoms in the organic layers obtained. Moreover, it was observed that the larger the end group of the ethynyl derivative, the thinner the thickness of the ultrathin polymeric layers as measured by both SXPS and SEM techniques after low and high current flow respectively. For the first time, these new types of ultrathin organic layers on Si surfaces were investigated using infrared spectroscopic ellipsometry (IRSE). The different possible reaction pathways are discussed.

  3. Integration of Faradaic electrochemical impedance spectroscopy into a scalable surface plasmon biosensor for in tandem detection.

    PubMed

    Hong, Brandon; Sun, Alexander; Pang, Lin; Venkatesh, A G; Hall, Drew; Fainman, Yeshaiahu

    2015-11-16

    We present an integrated label-free biosensor based on surface plasmon resonance (SPR) and Faradaic electrochemical impedance spectroscopy (f-EIS) sensing modalities, for the simultaneous detection of biological analytes. Analyte detection is based on the angular spectroscopy of surface plasmon resonance and the extraction of charge transfer resistance values from reduction-oxidation reactions at the gold surface, as responses to functionalized surface binding events. To collocate the measurement areas and fully integrate the modalities, holographically exposed thin-film gold SPR-transducer gratings are patterned into coplanar electrodes for tandem impedance sensing. Mutual non-interference between plasmonic and electrochemical measurement processes is shown, and using our scalable and compact detection system, we experimentally demonstrate biotinylated surface capture of neutravidin concentrations as low as 10 nM detection, with a 5.5 nM limit of detection.

  4. 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.``

  5. 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. PMID:25711524

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

    PubMed

    Armendáriz-Vidales, Georgina; Frontana, Carlos

    2014-09-01

    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. PMID:25007856

  7. 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.

  8. Electrochemical behavior of nano and femtosecond laser textured titanium alloy for implant surface modification.

    PubMed

    Jeong, Yong-Hoon; Kim, Won-Gi; Choe, Han-Cheol

    2011-02-01

    In this study, the electrochemical behavior of nano and femtosecond laser textured titanium alloy for implant surface modification has been researched using the potentiostat equipment. Cp-Ti and Ti-6Al-4V alloy, located on X-Y motorized stage, were irradiated using femtosecond laser. The corrosion properties were examined by a potentiodynamic and AC impedance test.

  9. 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.

  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. 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.

  12. Impedance-derived electrochemical capacitance spectroscopy for the evaluation of lectin-glycoprotein binding affinity.

    PubMed

    Santos, Adriano; Carvalho, Fernanda C; Roque-Barreira, Maria-Cristina; Bueno, Paulo R

    2014-12-15

    Characterization of lectin-carbohydrate binding using label-free methods such as impedance-derived electrochemical capacitance spectroscopy (ECS) is desirable to evaluate specific interactions, for example, ArtinM lectin and horseradish peroxidase (HRP) glycoprotein, used here as a model for protein-carbohydrate binding affinity. An electroactive molecular film comprising alkyl ferrocene as a redox probe and ArtinM as a carbohydrate receptive center to target HRP was successfully used to determine the binding affinity between ArtinM and HRP. The redox capacitance, a transducer signal associated with the alkyl ferrocene centers, was obtained by ECS and used in the Langmuir adsorption model to obtain the affinity constant (1.6±0.6)×10(8) L mol(-1). The results shown herein suggest the feasibility of ECS application for lectin glycoarray characterization. PMID:24994505

  13. Impedance-derived electrochemical capacitance spectroscopy for the evaluation of lectin-glycoprotein binding affinity.

    PubMed

    Santos, Adriano; Carvalho, Fernanda C; Roque-Barreira, Maria-Cristina; Bueno, Paulo R

    2014-12-15

    Characterization of lectin-carbohydrate binding using label-free methods such as impedance-derived electrochemical capacitance spectroscopy (ECS) is desirable to evaluate specific interactions, for example, ArtinM lectin and horseradish peroxidase (HRP) glycoprotein, used here as a model for protein-carbohydrate binding affinity. An electroactive molecular film comprising alkyl ferrocene as a redox probe and ArtinM as a carbohydrate receptive center to target HRP was successfully used to determine the binding affinity between ArtinM and HRP. The redox capacitance, a transducer signal associated with the alkyl ferrocene centers, was obtained by ECS and used in the Langmuir adsorption model to obtain the affinity constant (1.6±0.6)×10(8) L mol(-1). The results shown herein suggest the feasibility of ECS application for lectin glycoarray characterization.

  14. 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.

  15. Two-Dimensional Imaging of Potential Waves in Electrochemical Systems by Surface Plasmon Microscopy

    NASA Astrophysics Data System (ADS)

    Flatgen, Georg; Krischer, Katharina; Pettinger, Bruno; Doblhofer, Karl; Junkes, Heinz; Ertl, Gerhard

    1995-08-01

    The potential dependence of resonance conditions for the excitation of surface plasmons was exploited to obtain two-dimensional images of the potential distribution of an electrode with high temporal resolution. This method allows the study of spatiotemporal patterns in electrochemical systems. Potential waves traveling across the electrode with a speed on the order of meters per second were observed in the bistable regime of an oscillatory electrochemical reaction. This velocity is close to that of excitation waves in nerve fibers and is far greater than the velocity of reaction-diffusion waves observed in other chemical systems.

  16. Electrochemical surface plasmon resonance sensor based on two-electrode configuration

    NASA Astrophysics Data System (ADS)

    Zhang, Bing; Li, Yazhuo; Dong, Wei; Wen, Yizhang; Pang, Kai; Zhan, Shuyue; Wang, Xiaoping

    2016-10-01

    To obtain detailed information about electrochemistry reactions, a two-electrode electrochemical surface plasmon resonance (EC-SPR) sensor has been proposed. We describe the theory of potential modulation for this novel sensor and determine the factors that can change the SPR resonance angle. The reference electrode in three-electrode configuration was eliminated, and comparing with several other electrode materials, activated carbon (AC) is employed as the suitable counter electrode for its potential stability. Just like three-electrode configuration, the simpler AC two-electrode system can also obtain detailed information about the electrochemical reactions.

  17. Electrochemical reactivity of aromatic molecules at nanometer-sized surface domains: from Pt(hkl) single crystal electrodes to preferentially oriented platinum nanoparticles.

    PubMed

    Rodríguez-López, Margarita; Solla-Gullón, Jose; Herrero, Enrique; Tuñón, Paulino; Feliu, Juan M; Aldaz, Antonio; Carrasquillo, Arnaldo

    2010-02-24

    This manuscript compares the electrochemically controlled adsorption of hydroquinone-derived adlayers and their reductive desorption from nanometer-sized Pt(111) domains present on the surface (i) of model stepped single-crystal electrodes and (ii) of preferentially oriented Pt nanoparticles. The results obtained using a stepped surface series, i.e., Pt(S)[(n - 1)(111)x(110)], suggest that in the presence of 2 mM H(2)Q((aq)) the electrochemically detected desorption-adsorption process takes place selectively from ordered Pt(111) domains present as terraces, while being precluded at other available surface sites, i.e., Pt(110) steps, where adsorption takes place irreversibly. This domain-selective electroanalytical detection scheme is employed later to selectively monitor desorption-adsorption of hydroquinone-derived adlayers from ordered, nanometer-scaled Pt(111) domains on the surface of preferentially oriented Pt nanoparticles, confirming the existence of well-ordered (111) domains on the surface of the Pt nanoparticles. A good correlation is noted between the electrochemical behavior at well-ordered Pt(hkl) surfaces and at preferentially oriented Pt nanoparticles. Key learnings and potential applications are discussed. The results demonstrate the technical feasibility of performing domain-selective decapping of nanoparticles by handle of an externally controlled parameter, i.e., the applied potential.

  18. DNA nanostructure-decorated surfaces for enhanced aptamer-target binding and electrochemical cocaine sensors.

    PubMed

    Wen, Yanli; Pei, Hao; Wan, Ying; Su, Yan; Huang, Qing; Song, Shiping; Fan, Chunhai

    2011-10-01

    The sensitivity of aptamer-based electrochemical sensors is often limited by restricted target accessibility and surface-induced perturbation of the aptamer structure, which arise from imperfect packing of probes on the heterogeneous and locally crowded surface. In this study, we have developed an ultrasensitive and highly selective electrochemical aptamer-based cocaine sensor (EACS), based on a DNA nanotechnology-based sensing platform. We have found that the electrode surface decorated with an aptamer probe-pendant tetrahedral DNA nanostructure greatly facilitates cocaine-induced fusion of the split anticocaine aptamer. This novel design leads to a sensitive cocaine sensor with a remarkably low detection limit of 33 nM. It is also important that the tetrahedra-decorated surface is protein-resistant, which not only suits the enzyme-based signal amplification scheme employed in this work, but ensures high selectivity of this sensor when deployed in sera or other adulterated samples.

  19. Potent 5-nitrofuran derivatives inhibitors of Trypanosoma cruzi growth: Electrochemical, spectroscopic and biological studies

    NASA Astrophysics Data System (ADS)

    Maria Aravena, C.; Claudio Olea, A.; Cerecetto, Hugo; González, Mercedes; Maya, Juan Diego; Rodríguez-Becerra, Jorge

    2011-07-01

    Cyclic voltammetry and electron spin resonance techniques were used in the investigation of several potential antiprotozoal containing thiosemicarbazone and carbamate nitrofurans. In the electrochemical behaviour, a self-protonation process involving the nitro group was observed. The reactivity of the nitro anion radical for these derivatives with glutathione, a biological relevant thiol, was also studied in means of cyclic voltammetry. These studies demonstrated that glutathione could react with radical species from 5-nitrofuryl system. Furthermore, from the voltammetric results, some parameters of biological significance as E71 (indicative of the biological nitro anion radical formation), and K (thermodynamic indicator the of oxygen redox cycling) have been calculated. We also evaluated the stability of the nitro anion radical in terms of the dimerization constant ( kd). The nitrofuran-free radicals from cyclic voltammetry were characterized by electron spin resonance. A clear dependence between both the thiosemicarbazone or carbamate substructure and the length of the linker, furyl- or furylpropenyl-spacer, and the delocalization of the unpaired electron was observed. Through of biological assays we obtained important parameters that account for the selective anti-trypanosomal activity of these derivatives. The trypomastigote viability study showed that all derivatives are as active as in the epimastigote form of the parasite in a doses dependent manner.

  20. 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.

  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. 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).

  4. 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. PMID:26652467

  5. 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.

  6. 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.

  7. Electrochemical Instability of Phosphonate-Derivatized, Ruthenium(III) Polypyridyl Complexes on Metal Oxide Surfaces.

    PubMed

    Hyde, Jacob T; Hanson, Kenneth; Vannucci, Aaron K; Lapides, Alexander M; Alibabaei, Leila; Norris, Michael R; Meyer, Thomas J; Harrison, Daniel P

    2015-05-13

    The oxidative stability of the molecular components of dye-sensitized photoelectrosynthesis cells for solar water splitting remains to be explored systematically. We report here the results of an electrochemical study on the oxidative stability of ruthenium(II) polypyridyl complexes surface-bound to fluorine-doped tin oxide electrodes in acidic solutions and, to a lesser extent, as a function of pH and solvent with electrochemical monitoring. Desorption occurs for the Ru(II) forms of the surface-bound complexes with oxidation to Ru(III) enhancing both desorption and decomposition. Based on the results of long-term potential hold experiments with cyclic voltammetry monitoring, electrochemical oxidation to Ru(III) results in slow decomposition of the complex by 2,2'-bipyridine ligand loss and aquation and/or anation. A similar pattern of ligand loss was also observed for a known chromophore-catalyst assembly for both electrochemical water oxidation and photoelectrochemical water splitting. Our results are significant in identifying the importance of enhancing chromophore stability, or at least transient stability, in oxidized forms in order to achieve stable performance in aqueous environments in photoelectrochemical devices. PMID:25871342

  8. High-performance liquid chromatographic determination of linoleic acid peroxide-derived radicals using electrochemical detection.

    PubMed

    Iwahashi, H

    2000-12-29

    High-performance liquid chromatography-electrochemical detection (HPLC-ED) was applied to detect 13-hydroperoxide octadecadienoic acid (13-HPODE)-derived radicals such as the pentyl radical and octanoic acid radical. The 13-HPODE-derived radicals were successfully detected using HPLC-ED by the combined use of the spin-trapping technique with alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone (4-POBN). The 4-POBN-pentyl radical adduct was detected at the retention time of 18.2 +/- 0.3 min on the elution profile of HPLC-ED with an ODS column (15 cm x 4.6 mm I.D.) using a flow-rate of 1.0 ml/min with 50 mM ammonium acetate in 29% (v/v) aqueous acetonitrile. The 4-POBN-octanoic acid radical adduct was also detected at the retention time of 13.7 +/- 0.7 min using a flow-rate of 1.0 ml/min with 50 mM ammonium acetate in 14% (v/v) aqueous acetonitrile. The concentrations of the 4-POBN radical adducts were determined using HPLC-ED without an internal standard. HPLC-ED is 100 times as sensitive as HPLC-electron spin resonance (ESR) under the ESR and ED conditions employed here. Even 1.8 pmol of the 4-POBN-pentyl (or octanoic acid) radical adduct was detectable using PMID:11204234

  9. Electrochemical Surface Plasmon Resonance Fiber-Optic Sensor: In Situ Detection of Electroactive Biofilms.

    PubMed

    Yuan, Yong; Guo, Tuan; Qiu, Xuhui; Tang, Jiahuan; Huang, Yunyun; Zhuang, Li; Zhou, Shungui; Li, Zhaohui; Guan, Bai-Ou; Zhang, Xuming; Albert, Jacques

    2016-08-01

    Spectroelectrochemistry has been found to be an efficient technique for revealing extracellular electron transfer (EET) mechanism of electroactive biofilms (EABs). Herein, we propose a novel electrochemical surface plasmon resonance (EC-SPR) optical fiber sensor for monitoring EABs in situ. The sensor uses a tilted fiber Bragg grating (TFBG) imprinted in a commercial single-mode fiber and coated with nanoscale gold film for high-efficiency SPR excitation. The wavelength shift of the surface plasmon resonance (SPR) over the fiber surface clearly identifies the electrochemical activity of the surface localized (adjacent to the electrode interface) bacterial cells in EABs, which differs from the "bulk" detections of the conventional electrochemical measurements. A close relationship between the variations of redox state of the EABs and the changes of the SPR under potentiostatic conditions has been achieved, pointing to a new way to study the EET mechanism of the EABs. Benefiting from its compact size, high sensitivity, and ease of use, together with remote operation ability, the proposed sensor opens up a multitude of opportunities for monitoring EABs in various hard-to-reach environments. PMID:27214753

  10. 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. PMID:25924305

  11. 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.

  12. Electrochemical machining of super-hydrophobic Al surfaces and effect of processing parameters on wettability

    NASA Astrophysics Data System (ADS)

    Song, Jin-long; Xu, Wen-ji; Liu, Xin; Lu, Yao; Sun, Jing

    2012-09-01

    Super-hydrophobic aluminum (Al) surfaces were successfully fabricated via electrochemical machining in neutral NaClO3 electrolyte and subsequent fluoroalkylsilane (FAS) modification. The effects of the processing time, processing current density, and electrolyte concentration on the wettability, morphology, and roughness were studied. The surface morphology, chemical composition, and wettability of the Al surfaces were investigated using scanning electron microscopy (SEM) equipped with energy-dispersive spectroscopy (EDS), white-light interferometry, roughness measurements, X-ray diffraction (XRD), Fourier-transform infrared spectrometry (FTIR), and optical contact angle measurements. The results show that hierarchical rough structures and low surface energy films were present on the Al surfaces after electrochemical machining and FAS modification. The combination of the rough structures and the low surface energy materials plays a crucial role in achieving super-hydrophobicity. Compared with the anodic oxidation and chemical etching method, the method proposed in our work does not require strong acid or alkali, and causes less harm to the environment and operators but with high processing efficiency. The rough structures required by the super-hydrophobic surfaces were obtained at 30-s processing time and the best super-hydrophobicity with 164.6∘ water contact angle and 2∘ tilting angle was obtained at 360 s. The resulting super-hydrophobic Al surfaces have a long-time stability in air and an excellent resistance to corrosive liquids.

  13. Electrochemical reactions at surfaces. (Latest citations from the NTIS Bibliographic database). Published Search

    SciTech Connect

    Not Available

    1993-10-01

    The bibliography contains citations concerning electrode processes, mostly in aqueous solutions, but also involving some nonaqueous electrolytes. Included are those reactions associated with battery electrodes, fuel cells, and catalyst reactions, with some molten salt processes. The reports cover electrochemical corrosion studies, chemisorption, theoretical analysis of surface reactions, electrical double layer, measurement techniques, and some applications of the electrode processes. (Contains 250 citations and includes a subject term index and title list.)

  14. Electrochemical interfacial influences on deoxygenation and hydrogenation reactions in CO reduction on a Cu(100) surface.

    PubMed

    Sheng, Tian; Lin, Wen-Feng; Sun, Shi-Gang

    2016-06-01

    Electroreduction of CO2 to hydrocarbons on a copper surface has attracted much attention in the last few decades for providing a sustainable way for energy storage. During the CO2 and further CO electroreduction processes, deoxygenation that is C-O bond dissociation, and hydrogenation that is C-H bond formation, are two main types of surface reactions catalyzed by the copper electrode. In this work, by performing the state-of-the-art constrained ab initio molecular dynamics simulations, we have systematically investigated deoxygenation and hydrogenation reactions involving two important intermediates, COHads and CHOads, under various conditions of (i) on a Cu(100) surface without water molecules, (ii) at the water/Cu(100) interface and (iii) at the charged water/Cu(100) interface, in order to elucidate the electrochemical interfacial influences. It has been found that the electrochemical interface can facilitate considerably the C-O bond dissociation via changing the reaction mechanisms. However, C-H bond formation has not been affected by the presence of water or electrical charge. Furthermore, the promotional roles of an aqueous environment and negative electrode potential in deoxygenation have been clarified, respectively. This fundamental study provides an atomic level insight into the significance of the electrochemical interface towards electrocatalysis, which is of general importance for understanding electrochemistry. PMID:27211005

  15. 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.

  16. Structure and Dynamics of the Au(111) Surface in an Electrochemical Enviroment

    NASA Astrophysics Data System (ADS)

    Collini, John; Liu, Yihua; McDonough, Bryanne; Pierce, Michael; You, Hoydoo; Komanicky, Vladimir; Barbour, Andi

    The Au(111) surface possesses a well-known herringbone surface reconstruction pattern. However, the character of the reconstruction's response to external variables is not completely understood due to the limited amount of kinetics and dynamics studies of the surface in different environments. Here, we present in-situ x-ray scattering measurements from the Advanced Photon Source at Argonne National Laboratory of the Au(111) surface in a controllable electrochemical environment of weak NaF solution. Crystal truncation rod (CTR) measurements were taken to examine how the average surface properties and overall structure change with cell voltage. X-ray photon correlation spectroscopy (XPCS) measurements were also taken to examine how the dynamics of the surface change with voltage. The relation between applied potential, average kinetics, and microstate dynamics will be discussed. Funding provided by Research Corporation for Science Advancement. Work done at the Advanced Photon Source supported by the U.S. Department of Energy.

  17. 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.

  18. 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.

  19. Aptamer-based electrochemical detection of picomolar platelet-derived growth factor directly in blood serum.

    PubMed

    Lai, Rebecca Y; Plaxco, Kevin W; Heeger, Alan J

    2007-01-01

    We report an electrochemical, aptamer-based (E-AB) sensor for the detection of platelet-derived growth factor (PDGF) directly in blood serum. The E-AB approach employs alternating current voltammetry to monitor target-induced folding in a methylene blue-modified, PDGF-binding aptamer. The sensor is sensitive, highly selective, and essentially reagentless: we readily detect the BB variant of PDGF at 1 nM directly in undiluted, unmodified blood serum and at 50 pM (1.25 ng/mL) in serum-diluted 2-fold with aqueous buffer. The sensitivity and selectivity achieved by this sensor match or significantly exceed those of the best analogous optical approaches. For example, the detection limit attained in 50% serum is achieved against a >25 million-fold excess of contaminating blood proteins and represents a 4 order of magnitude improvement over the most sensitive optical PDGF aptasensor reported to date. Moreover, the E-AB sensor combines these promising attributes in a platform that is reusable, label-free, and electronic. Given these advantages, E-AB sensors appear well suited for implementation in portable microdevices directed at the direct detection of proteins and small molecules in complex, largely unprocessed clinical samples.

  20. 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.

  1. Electrochemical Characterization of Protein Adsorption onto YNGRT-Au and VLGXE-Au Surfaces

    PubMed Central

    Trzeciakiewicz, Hanna; Esteves-Villanueva, Jose; Soudy, Rania; Kaur, Kamaljit; Martic-Milne, Sanela

    2015-01-01

    The adsorption of the proteins CD13, mucin and bovine serum albumin on VLGXE-Au and YNGRT-Au interfaces was monitored by electrochemical impedance spectroscopy in the presence of [Fe(CN)6]3−/4−. The hydrophobicity of the Au surface was tailored using specific peptides, blocking agents and diluents. The combination of blocking agents (ethanolamine or n-butylamine) and diluents (hexanethiol or 2-mercaptoethanol) was used to prepare various peptide-modified Au surfaces. Protein adsorption onto the peptide-Au surfaces modified with the combination of n-butylamine and hexanethiol produced a dramatic decrease in the charge transfer resistance, Rct, for all three proteins. In contrast, polar peptide-surfaces induced a minimal change in Rct for all three proteins. Furthermore, an increase in Rct was observed with CD13 (an aminopeptidase overexpressed in certain cancers) in comparison to the other proteins when the VLGXE-Au surface was modified with n-butylamine as a blocking agent. The electrochemical data indicated that protein adsorption may be modulated by tailoring the peptide sequence on Au surfaces and that blocking agents and diluents play a key role in promoting or preventing protein adsorption. The peptide-Au platform may also be used for targeting cancer biomarkers with designer peptides. PMID:26262621

  2. A plasmon-driven selective surface catalytic reaction revealed by surface-enhanced Raman scattering in an electrochemical environment.

    PubMed

    Cui, Lin; Wang, Peijie; Fang, Yurui; Li, Yuanzuo; Sun, Mengtao

    2015-07-06

    Plasmonic catalytic reactions of molecules with single amine or nitro groups have been investigated in recent years. However, plasmonic catalysis of molecules with multiple amine and/or nitro groups is still unknown. In this paper, plasmon-driven catalytic reactions of 4,4'-dinitroazobenzene (DNAB), 4,4'-diaminoazobenzene (DAAB) and 4-nitro-4'-aminoazobenzene (NAAB) are investigated using electrochemical surface-enhanced Raman scattering (SERS) spectroscopy. The results reveal that a plasmon-driven reduction reaction occurred for DNAB and NAAB in which the NO2 group was reduced to NH2, while the plasmon-driven oxidation reaction of NH2 did not occur. This result demonstrates that plasmon-driven reduction reactions are much easier than plasmon-driven oxidization reactions in electrochemical environments. The molecular resonance may also play an important role in plasmon-driven catalytic reactions. These findings provide us with a deeper understanding of plasmon-driven catalytic reactions.

  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. 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.

  5. Critical View on graphene oxide production and its transfer to surfaces aiming electrochemical applications.

    PubMed

    Timm, Ronaldo Adriano; Kisner, Alexandre; Bassetto, Victor Costa; Kubota, Lauro Tatsuo

    2014-09-01

    Graphene and related materials has been studied aiming their use in several applications including electrochemical sensing systems for a large number of different analytes. However, there have been proportionally only a few studies discussing deeply the implications of the different variables that could be tuned in the preparations of these materials for the development of the electrochemical platforms. In this review it is discussed how the size, number of layers, crystallinity and purity of the graphite starting material affects the final graphene oxide (GO) and reduced graphene oxide (rGO) prepared by chemical exfoliation. The exfoliation process and the most frequently applied transfer methods used to prepare thin films of GO and rGO on surfaces/electrodes of sensing platforms are also discussed. The electrochemical behavior of these materials is evaluated as a role of surface organization and adsorption. Considering the parameters previously presented, it is outlined some of the most relevant sensors and biosensor systems, which employ graphene related materials and attempts to explore different possibilities of deposition.

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

    PubMed Central

    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/cm2, electrolysis time of 103.27 min, and electrolyte (NaCl) concentration of 1.67 g/L, respectively. PMID:26491716

  7. 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. PMID:26491716

  8. Supramolecular control of photochemical and electrochemical properties of two oligothiophene derivatives at the air/water interface.

    PubMed

    Selector, Sophiya; Fedorova, Olga; Lukovskaya, Elena; Anisimov, Alexander; Fedorov, Yuri; Tarasova, Nina; Raitman, Oleg; Fages, Frederic; Arslanov, Vladimir

    2012-02-01

    Two geometric isomers of oligothiophene derivatives containing two crowned styryl fragments in 2- or 3-positions of thiophene rings are able to form stable monolayers on the water subphase. The organizing of crown-containing oligothiophenes in monolayers is guided by the π-stacking interaction of hydrophobic styrylthiophene fragments and interaction of hydrophilic macrocycles with the water subphase. The difference in structure of oligothiophene molecules leads to the formation of distinct monolayer architectures with various electrochemical and optical characteristics.

  9. 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.

  10. Electrochemical deposition and surface-initiated RAFT polymerization: protein and cell-resistant PPEGMEMA polymer brushes.

    PubMed

    Tria, Maria Celeste R; Grande, Carlos David T; Ponnapati, Ramakrishna R; Advincula, Rigoberto C

    2010-12-13

    This paper introduces a novel and versatile method of grafting protein and cell-resistant poly(poly ethylene glycol methyl ether methacrylate) (PPEGMEMA) brushes on conducting Au surface. The process started with the electrochemical deposition and full characterization of an electro-active chain transfer agent (CTA) on the Au surface. The electrochemical behavior of the CTA was investigated by cyclic voltammetry (CV) while the deposition and stability of the CTA on the surface were confirmed by ellipsometry, contact angle, and X-ray photoelectron spectroscopy (XPS). The capability of the electrodeposited CTA to mediate surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization on both the polymethyl methacrylate (PMMA; model polymer) and PPEGMEMA brushes was demonstrated by the increase in thicknesses of the films after polymerization. Contact angles also decreased with the incorporation of the more hydrophilic brushes. Significant changes in the morphologies of the films before and after polymerization were also observed with atomic force microscopy (AFM) analyses. Furthermore, XPS results showed an increase in the O 1s peak intensity relative to C 1s after polymerizations, which confirmed the grafting of polyethyleneglycol (PEG) bearing brushes. The ability of the PPEGMEMA-modified Au surface to resist nonspecific adhesion of proteins and cells was monitored and confirmed by XPS, ellipsometry, contact angle, AFM, and fluorescence imaging. The new method presented has potential application as robust protein and cell-resistant coatings for electrically conducting electrodes and biomedical devices.

  11. 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.

  12. Hyperspectrally-Resolved Surface Emissivity Derived Under Optically Thin Clouds

    NASA Technical Reports Server (NTRS)

    Zhou, Daniel K.; Larar, Allen M.; Liu, Xu; Smith, William L.; Strow, L. Larrabee; Yang, Ping

    2010-01-01

    Surface spectral emissivity derived from current and future satellites can and will reveal critical information about the Earth s ecosystem and land surface type properties, which can be utilized as a means of long-term monitoring of global environment and climate change. Hyperspectrally-resolved surface emissivities are derived with an algorithm utilizes a combined fast radiative transfer model (RTM) with a molecular RTM and a cloud RTM accounting for both atmospheric absorption and cloud absorption/scattering. Clouds are automatically detected and cloud microphysical parameters are retrieved; and emissivity is retrieved under clear and optically thin cloud conditions. This technique separates surface emissivity from skin temperature by representing the emissivity spectrum with eigenvectors derived from a laboratory measured emissivity database; in other words, using the constraint as a means for the emissivity to vary smoothly across atmospheric absorption lines. Here we present the emissivity derived under optically thin clouds in comparison with that under clear conditions.

  13. Surface modification and electrochemical properties of activated carbons for supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Yang, Dan; Qiu, Wenmei; Xu, Jingcai; Han, Yanbing; Jin, Hongxiao; Jin, Dingfeng; Peng, Xiaoling; Hong, Bo; Li, Ji; Ge, Hongliang; Wang, Xinqing

    2015-12-01

    Modifications with different acids (HNO3, H2SO4, HCl and HF, respectively) were introduced to treat the activated carbons (ACs) surface. The microstructures and surface chemical properties were discussed by X-ray diffraction (XRD), thermogravimetric analysis (TGA), ASAP, Raman spectra and Fourier transform infrared (FTIR) spectra. The ACs electrode-based supercapacitors were assembled with 6 mol ṡ L-1 KOH electrolyte. The electrochemical properties were studied by galvanostatic charge-discharge and cyclic voltammetry. The results indicated that although the BET surface area of modified ACs decreased, the functional groups were introduced and the ash contents were reduced on the surface of ACs, receiving larger specific capacitance to initial AC. The specific capacitance of ACs modified with HCl, H2SO4, HF and HNO3 increased by 31.4%, 23%, 21% and 11.6%, respectively.

  14. Electrochemical Glucose Biosensor Based on Glucose Oxidase Displayed on Yeast Surface.

    PubMed

    Wang, Hongwei; Lang, Qiaolin; Liang, Bo; Liu, Aihua

    2015-01-01

    The conventional enzyme-based biosensor requires chemical or physical immobilization of purified enzymes on electrode surface, which often results in loss of enzyme activity and/or fractions immobilized over time. It is also costly. A major advantage of yeast surface display is that it enables the direct utilization of whole cell catalysts with eukaryote-produced proteins being displayed on the cell surface, providing an economic alternative to traditional production of purified enzymes. Herein, we describe the details of the display of glucose oxidase (GOx) on yeast cell surface and its application in the development of electrochemical glucose sensor. In order to achieve a direct electrochemistry of GOx, the entire cell catalyst (yeast-GOx) was immobilized together with multiwalled carbon nanotubes on the electrode, which allowed sensitive and selective glucose detection. PMID:26060079

  15. Rapid fabrication of superhydrophobic surfaces on copper substrates by electrochemical machining

    NASA Astrophysics Data System (ADS)

    Song, Jinlong; Xu, Wenji; Lu, Yao; Fan, Xujuan

    2011-10-01

    Hierarchical micrometer-nanometer-scale binary rough structures were fabricated on copper substrates by electrochemical machining in a neutral NaCl electrolyte. The rough structures are composed of the micrometer scale potato-like structures and the nanometer scale cube-like structures. After modified by the fluoroalkylsilane, the copper surfaces reached superhydrophobicity with a water contact angle of 164.3° and a water tilting angle less than 9°. This method has a high processing efficiency which can take just 3 s to fabricate the roughness required by the superhydrophobic surface. The effect of the processing time on wettability of the copper surfaces was investigated in this paper. The possible mechanism of the formation of the hierarchical roughness was also proposed, and the wettability of the copper surfaces was discussed on the basis of the Cassie-Baxter theory.

  16. Magnetohydrodynamic motion of a colloidal sphere with self-electrochemical surface reactions in a spherical cavity.

    PubMed

    Hsieh, Tzu H; Keh, Huan J

    2013-02-21

    An analytical study is presented for the magnetic-field-induced motion of a colloidal sphere with spontaneous electrochemical reactions on its surface situated at the center of a spherical cavity filled with an electrolyte solution at the quasi-steady state. The zeta potential associated with the particle surface may have an arbitrary distribution, whereas the electric double layers adjoining the particle and cavity surfaces are taken to be thin relative to the particle size and the spacing between the solid surfaces. The electric current and magnetic flux density distributions are solved for the particle and fluid phases of arbitrary electric conductivities and magnetic permeabilities. Applying a generalized reciprocal theorem to the Stokes equations with a Lorentz force term resulting from these density distributions for the fluid motion, we obtain explicit formulas for the translational and angular velocities of the colloidal sphere valid for all values of the particle-to-cavity size ratio. The particle velocities decrease monotonically with an increase in this size ratio. For the limiting case of an infinitely large cavity, our result reduces to the relevant solution for an unconfined spherical particle. The boundary effect on the movement of the particle with interfacial self-electrochemical reactions induced by the magnetohydrodynamic force is equivalent to that in sedimentation and much stronger than that in general phoretic motions.

  17. An algorithm for simulation of electrochemical systems with surface-bulk coupling strategies

    NASA Astrophysics Data System (ADS)

    Buoni, Matthew; Petzold, Linda

    2010-01-01

    In Buoni and Petzold (2007) [13] we described a new algorithm for simulation of electrochemical systems on two-dimensional irregular, time-dependent domains. Here we show how to extend the algorithm to three dimensions. We demonstrate our three-dimensional algorithm by simulating copper electrodeposition into a via structure. This problem poses challenges for the coupling of the dilute electrolyte (bulk) model to the surface dynamics model, which involves a complex network of reactions. To handle this coupling, we introduce a new and highly effective semi-implicit method.

  18. Atmospheric and electrochemical oxidation of the surface of chalcopyrite (CuFeS 2)

    NASA Astrophysics Data System (ADS)

    Yin, Q.; Kelsall, G. H.; Vaughan, D. J.; England, K. E. R.

    1995-03-01

    Atmospheric and electrochemical oxidation of the surface of chalcopyrite has been investigated using electrochemical techniques with subsequent surface analysis by X-ray photoelectron spectroscopy (XPS) and aqueous phase analysis by inductively coupled plasma-atomic emission spectrometry (ICPAES). The extent of atmospheric oxidation of chalcopyrite was assessed qualitatively by measuring the increase in the open circuit potential; quantitative estimation was made either by comparing the reduction charges of an atmospherically oxidised electrode with an unoxidised electrode and/or by comparing their oxidation charges at potentials less positive than those at which the main decomposition occurred. The oxidation current wave at potentials 0.1 V to 0.6 V vs. S.C.E. consists of two peaks, the charges of which vary with the surface roughness and the peak potentials of which vary with the electrolyte pH in the alkaline region. As the pH of the electrolyte was increased from 0 to 13, the mole ratio of sulfur to sulfate formed during the anodic oxidation decreased from 6:1 to 3.2:1 but remained around 6:1 as the potential was increased from 1.0 V to 1.8 V vs. S.C.E. in acidic electrolytes. A mechanism for the oxidation and passivation of chalcopyrite is proposed.

  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. Effect of surface microstructure on electrochemical performance of garnet solid electrolytes.

    PubMed

    Cheng, Lei; Chen, Wei; Kunz, Martin; Persson, Kristin; Tamura, Nobumichi; Chen, Guoying; Doeff, Marca

    2015-01-28

    Cubic garnet phases based on Al-substituted Li7La3Zr2O12 (LLZO) have high ionic conductivities and exhibit good stability versus metallic lithium, making them of particular interest for use in next-generation rechargeable battery systems. However, high interfacial impedances have precluded their successful utilization in such devices until the present. Careful engineering of the surface microstructure, especially the grain boundaries, is critical to achieving low interfacial resistances and enabling long-term stable cycling with lithium metal. This study presents the fabrication of LLZO heterostructured solid electrolytes, which allowed direct correlation of surface microstructure with the electrochemical characteristics of the interface. Grain orientations and grain boundary distributions of samples with differing microstructures were mapped using high-resolution synchrotron polychromatic X-ray Laue microdiffraction. The electrochemical characteristics are strongly dependent upon surface microstructure, with small grained samples exhibiting much lower interfacial resistances and better cycling behavior than those with larger grain sizes. Low area specific resistances of 37 Ω cm(2) were achieved; low enough to ensure stable cycling with minimal polarization losses, thus removing a significant obstacle toward practical implementation of solid electrolytes in high energy density batteries.

  1. Electrochemical behaviour and surface conductivity of niobium carbide-modified austenitic stainless steel bipolar plate

    NASA Astrophysics Data System (ADS)

    Wang, Lixia; Sun, Juncai; Kang, Bin; Li, Song; Ji, Shijun; Wen, Zhongsheng; Wang, Xiaochun

    2014-01-01

    A niobium carbide diffusion layer with a cubic NbC phase surface layer (∼6 μm) and a Nb and C diffusion subsurface layer (∼1 μm) is fabricated on the surface of AISI 304 stainless steel (304 SS) bipolar plate in a proton exchange membrane fuel cell (PEMFC) using plasma surface diffusion alloying. The electrochemical behaviour of the niobium carbide diffusion-modified 304 SS (Nb-C 304 SS) is investigated in simulated PEMFC environments (0.5 M H2SO4 and 2 ppm HF solution at 80 °C). Potentiodynamic, potentiostatic polarisation and electrochemical impedance spectroscopy measurements reveal that the niobium carbide diffusion layer considerably improves the corrosion resistance of 304 SS compared with untreated samples. The corrosion current density of Nb-C 304 SS is maintained at 0.058 μA cm-2 and 0.051 μA cm-2 under simulated anodic and cathodic conditions, respectively. The interfacial contact resistance of Nb-C 304 SS is 8.47 mΩ cm2 at a compaction force of 140 N cm-2, which is significantly lower than that of the untreated sample (100.98 mΩ cm2). Moreover, only a minor increase in the ICR of Nb-C 304 SS occurs after 10 h potentiostatic tests in both cathodic and anodic environments.

  2. Electrocatalytic Oxidation Properties of Ascorbic Acid at Poly(3, 4-ethylenedioxythiophene) Films Studied by Electrochemical-Surface Plasmon Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Baba, Akira; Sano, Yohsuke; Ohdaira, Yasuo; Shinbo, Kazunari; Kato, Keizo; Kaneko, Futao

    In this report, we demonstrate electrocatalytic oxidation properties of ascorbic acid at poly(3, 4-ethylenedioxythiophene) (PEDOT) thin films in view of their potential application for bio-sensing devices. PEDOT thin films were deposited on gold thin films by electropolymerization of EDOT monomer in acetonitrile solvent. In-situ electrochemical-surface plasmon resonance spectroscopy (EC-SPR) was used to detect both electrochemical and optical signals upon an injection of ascorbic acid.

  3. 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

  4. Voltammetric detection of damage to DNA caused by nitro derivatives of fluorene using an electrochemical DNA biosensor.

    PubMed

    Vyskocil, Vlastimil; Labuda, Ján; Barek, Jirí

    2010-05-01

    An electrochemical DNA biosensor based on the screen printed carbon paste electrode (SPCPE) with an immobilized layer of calf thymus double-stranded DNA has been used for in vitro investigation of the interaction between genotoxic nitro derivatives of fluorene (namely 2-nitrofluorene and 2,7-dinitrofluorene) and DNA. Two types of DNA damage have been detected at the DNA/SPCPE biosensor: first, that caused by direct association of the nitrofluorenes, for which an intercalation association has been found using the known DNA intercalators [Cu(phen)(2)](2+) and [Co(phen)(3)](3+) as competing agents, and, second, that caused by short-lived radicals generated by electrochemical reduction of the nitro group (observable under specific conditions only). PMID:20186538

  5. Surface active properties of chitosan and its derivatives.

    PubMed

    Elsabee, Maher Z; Morsi, Rania Elsayed; Al-Sabagh, A M

    2009-11-01

    This review discusses the definition of surface active agents and specifically natural polymeric surface active agents. Chitosan by itself was found to have weak surface activity since it has no hydrophobic segments. Chemical modifications of chitosan could improve such surface activity. This is achieved by introducing hydrophobic substituents in its glucosidic group. Several examples of chitosan derivatives with surfactant activity have been surveyed. The surface active polymers form micelles and aggregates which have enormous importance in the entrapment of water-insoluble drugs and consequently applications in the controlled drug delivery and many biomedical fields. Chitosan also interacts with several substrates by electrostatic and hydrophobic interactions with considerable biomedical applications.

  6. Surface Composition, Work Function, and Electrochemical Characteristics of Gallium-Doped Zinc Oxide

    SciTech Connect

    Ratcliff, E. L.; Sigdel, A. K.; Macech, M. R.; Nebesny, K.; Lee, P. A.; Ginley, D. S.; Armstrong, N. R.; Berry, J. J.

    2012-06-30

    Gallium-doped zinc oxide (GZO) possesses the electric conductivity, thermal stability, and earth abundance to be a promising transparent conductive oxide replacement for indium tin oxide electrodes in a number of molecular electronic devices, including organic solar cells and organic light emitting diodes. The surface chemistry of GZO is complex and dominated by the hydrolysis chemistry of ZnO, which influences the work function via charge transfer and band bending caused by adsorbates. A comprehensive characterization of the surface chemical composition and electrochemical properties of GZO electrodes is presented, using both solution and surface adsorbed redox probe molecules. The GZO surface is characterized using monochromatic X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy after the following pretreatments: (i) hydriodic acid etch, (ii) potassium hydroxide etch, (iii) RF oxygen plasma etching, and (iv) high-vacuum argon-ion sputtering. The O 1s spectra for the GZO electrodes have contributions from the stoichiometric oxide lattice, defects within the lattice, hydroxylated species, and carbonaceous impurities, with relative near-surface compositions varying with pretreatment. Solution etching procedures result in an increase of the work function and ionization potential of the GZO electrode, but yield different near surface Zn:Ga atomic ratios, which significantly influence charge transfer rates for a chemisorbed probe molecule. The near surface chemical composition is shown to be the dominant factor in controlling surface work function and significantly influences the rate of electron transfer to both solution and tethered probe molecules.

  7. Assembly, characterization, and electrochemical properties of immobilized metal bipyridyl complexes on silicon(111) surfaces.

    PubMed

    Lattimer, Judith R C; Blakemore, James D; Sattler, Wesley; Gul, Sheraz; Chatterjee, Ruchira; Yachandra, Vittal K; Yano, Junko; Brunschwig, Bruce S; Lewis, Nathan S; Gray, Harry B

    2014-10-28

    Silicon(111) surfaces have been functionalized with mixed monolayers consisting of submonolayer coverages of immobilized 4-vinyl-2,2'-bipyridyl (1, vbpy) moieties, with the remaining atop sites of the silicon surface passivated by methyl groups. As the immobilized bipyridyl ligands bind transition metal ions, metal complexes can be assembled on the silicon surface. X-ray photoelectron spectroscopy (XPS) demonstrates that bipyridyl complexes of [Cp*Rh], [Cp*Ir], and [Ru(acac)2] were formed on the surface (Cp* is pentamethylcyclopentadienyl, acac is acetylacetonate). For the surface prepared with Ir, X-ray absorption spectroscopy at the Ir LIII edge showed an edge energy as well as post-edge features that were essentially identical with those observed on a powder sample of [Cp*Ir(bpy)Cl]Cl (bpy is 2,2'-bipyridyl). Charge-carrier lifetime measurements confirmed that the silicon surfaces retain their highly favorable photoelectronic properties upon assembly of the metal complexes. Electrochemical data for surfaces prepared on highly doped, n-type Si(111) electrodes showed that the assembled molecular complexes were redox active. However the stability of the molecular complexes on the surfaces was limited to several cycles of voltammetry.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Electrochemical impedance spectroscopy for graphene surface modification and protein translocation through the chemically modified graphene nanopore

    NASA Astrophysics Data System (ADS)

    Tiwari, Purushottam; Shan, Yuping; Wang, Xuewen; Darici, Yesim; He, Jin

    2014-03-01

    The multilayer graphene surface has been modified using mercaptohexadecanoic acid (MHA) and 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-750] (DPPE-PEG750). The surface modifications are evaluated using electrochemical impedance spectroscopy (EIS). EIS measurements show the better graphene surface passivation with DPPE-PEG750 than with MHA. After modification with ferritin, the MHA modified surface shows greater charge transfer resistance (Rct) change than DPPE-PEG750 modified surface. Based on these results the translocations of ferritin through modified graphene nanopore with diameter 5-20 nm are studied. The translocation is more successful through DPPE-PEG750 modified graphene nanopore. This concludes that that the attachment of ferritin to DPPE-PEG750 modified graphene nanopore is not significant compared to MHA modified pore for the ferritin translocation hindrance. These results nicely correlate with the EIS data for respective Rct change of ferritin modified surfaces. P. Tiwari would like to thank FIU School of Integrated Science & Humanity, College Arts & Sciences for the research assistantship.

  16. A Novel Sandwich Electrochemical Immunosensor Based on the DNA-Derived Magnetic Nanochain Probes for Alpha-Fetoprotein

    PubMed Central

    Gan, Ning; Jia, Liyong; Zheng, Lei

    2011-01-01

    One novel electrochemical immunosensor was constructed by immobilizing capture antibody of alpha-fetoprotein (AFP Ab1) on a nafion/nanogold-particle modified glassy carbon electrode. With a sandwich immunoassay, one DNA-derived magnetic nanoprobe, simplified as DNA/(ZMPs—HRP-AFP Ab2)n, was employed for the detection of AFP. The fabricated procedure of the proposed biosensor was characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The performance and factors influencing the performance of the biosensor were also evaluated. Under optimal conditions, the developed biosensor exhibited a well-defined electrochemical behavior toward the reduction of AFP ranging from 0.01 to 200 ng/mL with a detection limit of 4 pg/mL (S/N = 3). The biosensor was applied to the determination of AFP in serum with satisfactory results. It is important to note that the sandwich nanochainmodified electro-immunosensor provided an alternative substrate for the immobilization of other tumor markers. PMID:22013390

  17. An investigation of the electrochemical action of the epoxy zinc-rich coatings containing surface modified aluminum nanoparticle

    NASA Astrophysics Data System (ADS)

    Jalili, M.; Rostami, M.; Ramezanzadeh, B.

    2015-02-01

    Aluminum nanoparticle was modified with amino trimethylene phosphonic acid (ATMP). The surface characterization of the nanoparticles was done by X-ray photo electron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and thermal gravimetric analysis. The influence of the replacement of 2 wt% of zinc dust in the standard zinc-rich epoxy coating by nanoparticles on the electrochemical action of the coating was studied by electrochemical impedance spectroscopy (EIS) and salt spray tests. The morphology and phase composition of the zinc rich paints were evaluated by X-ray diffraction (XRD) and filed-emission scanning electron microscopy (FE-SEM). Results showed that the ATMP molecules successfully adsorbed on the surface of Al nanoparticles. Results obtained from salt spray and electrochemical measurements revealed that the addition of surface modified nanoparticles to the zinc rich coating enhanced its galvanic action and corrosion protection properties.

  18. Deriving surface albedo measurements from narrow band satellite data

    NASA Technical Reports Server (NTRS)

    Brest, Christopher L.; Goward, Samuel N.

    1987-01-01

    A target calibration procedure for obtaining surface albedo from satellite data is presented. The methodology addresses two key issues, the calibration of remotely-sensed, discrete wavelength, digital data and the derivation of an albedo measurement (defined over the solar short wave spectrum) from spectrally limited observations. Twenty-seven Landsat observations, calibrated with urban targets (building roof-tops and parking lots), are used to derive spatial and seasonal patterns of surface reflectance and albedo for four land cover types: city, suburb, farm and forest.

  19. 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.

  20. Kinetic study of electrochemically induced michael reactions of o-quinones with Meldrum's acid derivatives. Synthesis of highly oxygenated catechols.

    PubMed

    Nematollahi, D; Shayani-jam, H

    2008-05-01

    Electrochemical oxidation of catechols has been studied in the presence of Meldrum's acid derivatives as nucleophiles in aqueous solution, by means of cyclic voltammetry and controlled-potential coulometry. Catechols in the Michael addition reaction react with Meldrum's acids to form adducts that can undergo electrooxidation. Such products were obtained in good yields as confirmed by controlled potential electrosynthesis. Such products can be generated in aqueous solutions by means of electrosynthesis, using a carbon electrode in an undivided cell. Furthermore, the homogeneous rate constants of the chemical reaction interposed between electron transfers were estimated by comparing the experimental cyclic voltammetric curves with the digitally simulated ones.

  1. 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

  2. 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.

  3. 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.

  4. Surface interrogation of CoP(i) water oxidation catalyst by scanning electrochemical microscopy.

    PubMed

    Ahn, Hyun S; Bard, Allen J

    2015-01-21

    Despite exhaustive spectroscopic investigations on the CoPi oxygen-evolving catalyst over the past several years, little is known about the surface cobalt sites and intermediates in direct contact with water that are responsible for the actual catalysis. Many studies thus far have been limited to ex situ characterizations or bulk film measurements, often in the absence of solvent. Here we describe an investigation of the CoPi catalyst by surface interrogation scanning electrochemical microscopy (SI-SECM). This method should allow us to selectively study surface atoms separately from the bulk in a solvent-filled environment. By SI-SECM, independent titrations of surface Co(III) and Co(IV) were performed, yielding a direct measurement of the surface active-site density of a CoPi electrode (11 Co/nm(2)). The pseudo-first-order reaction rate constants of Co(III) and Co(IV) with water were determined to be 0.19 and >2 s(-1), respectively, through time-dependent titration measurements.

  5. Derivation of scaled surface reflectances from AVIRIS data

    NASA Technical Reports Server (NTRS)

    Gao, Bo-Cai; Heidebrecht, Kathleen B.; Goetz, Alexander F. H.

    1993-01-01

    A method for retrieving 'scaled surface reflectances' assuming horizontal surfaces having Lambertian reflectances from spectral data collected by Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) is presented here. In this method, the integrated water vapor amount on a pixel by pixel basis is derived from the 0.94 micron and 1.14 micron water vapor absorption features. The transmission spectra of H2O, CO2, O3, N2O, CO, CH4, and O2 in the 0.4-2.5 micron region are simulated. The scattering effect due to atmospheric molecules and aerosols is modeled with the 5S computer code. The AVIRIS radiances are divided by solar irradiances above the atmosphere to obtain the apparent reflectances. The scaled surface reflectances are derived from the apparent reflectances using the simulated atmospheric gaseous transmittances and the simulated molecular and aerosol scattering data. The scaled surface reflectances differ from the real surface reflectances by a multiplicative factor. In order to convert the scaled surface reflectances into real surface reflectances, the slopes and aspects of the surfaces must be known.

  6. 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.

  7. Heterogeneous Electrochemical Aptamer-Based Sensor Surfaces for Controlled Sensor Response.

    PubMed

    Schoukroun-Barnes, Lauren R; Glaser, Ethan P; White, Ryan J

    2015-06-16

    Structure-switching sensors utilize recognition elements that undergo a conformation change upon target binding that is converted into a quantitative signal. Electrochemical, aptamer-based sensors achieve detection of analytes through a conformation change in an electrode-bound, oligonucleotide aptamer by measuring changes in electron transfer efficiencies. The analytical performance of these sensors is related to the magnitude of the conformation change of the aptamer. The goal of the present work is to develop a general method to predictably tune the analytical performance (sensitivity and linear range) of electrochemical, aptamer-based sensors by utilizing a mixture of rationally designed aptamer sequences that are specific for the same target but with different affinities on the same electrode surface. To demonstrate control over sensor performance, we developed heterogeneous sensors for two representative small molecule targets (adenosine triphosphate and tobramycin). We demonstrate that mixtures of modified sequences can be used to tune the affinity, dynamic range, and sensitivity of the resulting sensors predicted by a bi-Langmuir-type isotherm.

  8. 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

  9. 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.

  10. Electrochemically induced surface metal migration in well-defined core-shell nanoparticles and its general influence on electrocatalytic reactions.

    PubMed

    Brodsky, Casey N; Young, Allison P; Ng, Ka Chon; Kuo, Chun-Hong; Tsung, Chia-Kuang

    2014-09-23

    Bimetallic nanoparticle catalysts provide enhanced activity, as combining metals allows tuning of electronic and geometric structure, but the enhancement may vary during the reaction because the nanoparticles can undergo metal migration under catalytic reaction conditions. Using cyclic voltammetry to track the surface composition over time, we carried out a detailed study of metal migration in a well-defined model Au-Pd core-shell nanocatalyst. When subjected to electrochemical conditions, Au migration from the core to the shell was observed. The effect of Pd shell thickness and electrolyte identity on the extent of migration was studied. Migration of metals during catalytic ethanol oxidation was found to alter the particle's surface composition and electronic structure, enhancing the core-shell particles' activity. We show that metal migration in core-shell nanoparticles is a phenomenon common to numerous electrochemical systems and must be considered when studying electrochemical catalysis.

  11. Potential Biosignificant Interest and Surface Activity of Efficient Heterocyclic Derivatives.

    PubMed

    El-Sayed, Refat; Althagafi, Ismail

    2016-01-01

    Some functionalized pyridine and fused system derivatives were synthesized using enaminonitrile derivative 5 as a starting material for the reaction, with various reagents under different conditions. Propoxylation of these compounds using different moles of propylene oxide (3, 5 and 7 moles) leads to a novel group of surface active agents. The antimicrobial and surface activities of the synthesized compounds were investigated. Most of the evaluated compounds proved to be active as antibacterial and antifungal agents and showed good surface activity, which makes them suitable for diverse applications such as the manufacturing of emulsifiers, cosmetics, drugs, pesticides, etc. Additionally, biodegradation testing exhibits significant breakdown within six to seven days, and hence, lowers the toxicity to human beings and becomes environmentally friendly.

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

    PubMed

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

    2012-10-01

    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. Effect of surface phosphorus functionalities of activated carbons containing oxygen and nitrogen on electrochemical capacitance

    PubMed Central

    Hulicova-Jurcakova, Denisa; Seredych, Mykola; Lu, Gao Qing; Kodiweera, N.K.A.C.; Stallworth, Phillip E.; Greenbaum, Steven; Bandosz, Teresa J.

    2009-01-01

    Micro/mesoporous activated carbons containing oxygen and phosphorus heteroatoms were modified by incorporation of nitrogen using melamine and urea precursors. The surface chemistry was analyzed by the means of elemental analysis, XPS, and 31P MAS NMR. The results indicate that upon the incorporation of nitrogen at high temperatures not only new species involving carbon/nitrogen/oxygen are formed but also the phosphorous environment is significantly altered. Both urea and melamine precursors have similar effects on formation of P–N and P–C bonds. These compounds, although present in small but measurable quantities seem to affect the performance of carbons in electrochemical capacitors. With an increase in the heterogeneity of phosphorus containing species and with a decrease in the content pyrophosphates the capacitance increases and the retention ratio of the capacitor is improved. PMID:20354586

  14. 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. PMID:27287100

  15. Electrochemical oxidation of aliphatic amines and their attachment to carbon and metal surfaces.

    PubMed

    Adenier, Alain; Chehimi, Mohamed M; Gallardo, Iluminada; Pinson, Jean; Vilà, Neus

    2004-09-14

    The electrochemical oxidation of aliphatic amines (primary, secondary, and tertiary) has been investigated by cyclic voltammetry and preparative electrolysis. The oxidation mechanisms have been established, and the lifetimes of the radical cations have been measured for secondary and tertiary amines. These results have been put in parallel with the attachment of amines to glassy carbon, Au, and Pt electrodes by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and infrared reflection-absorption spectroscopy (IRRAS). It is then possible to show that it is not the radical cation but the radical obtained after the deprotonation which reacts with the electrode surface. XPS results also point to the existence of a covalent bond between Au or Pt and the organic moiety.

  16. High-rate electrochemical capacitors based on ordered mesoporous silicon carbide-derived carbon.

    PubMed

    Korenblit, Yair; Rose, Marcus; Kockrick, Emanuel; Borchardt, Lars; Kvit, Alexander; Kaskel, Stefan; Yushin, Gleb

    2010-03-23

    Microporous carbons, produced by selective etching of metal carbides in a chlorine-containing environment, offer narrow distribution of micropores and one of the highest specific capacitances reported when used in electrical double layer capacitors (EDLC) with organic electrolytes. Previously, the small micropores in these carbons served as an impediment to ion transport and limited the power storage characteristics of EDLC. Here we demonstrate, for the first time, how the preparation and application of templated carbide-derived carbon (CDC) can overcome the present limitations and show the route for dramatic performance enhancement. The ordered mesoporous channels in the produced CDC serve as ion-highways and allow for very fast ionic transport into the bulk of the CDC particles. The enhanced transport led to 85% capacitance retention at current densities up to approximately 20 A/g. The ordered mesopores in silicon carbide precursor also allow the produced CDC to exhibit a specific surface area up to 2430 m(2)/g and a specific capacitance up to 170 F/g when tested in 1 M tetraethylammonium tetrafluoroborate solution in acetonitrile, nearly doubling the previously reported values. PMID:20180559

  17. 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

  18. 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.

  19. 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%.

  20. 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.

  1. Synthesis and electrochemical evaluation of an amorphous titanium dioxide derived from a solid state precursor

    NASA Astrophysics Data System (ADS)

    Joyce, Christopher D.; McIntyre, Toni; Simmons, Sade; LaDuca, Holly; Breitzer, Jonathan G.; Lopez, Carmen M.; Jansen, Andrew N.; Vaughey, J. T.

    Titanium oxides are an important class of lithium-ion battery electrodes owing to their good capacity and stability within the cell environment. Although most Ti(IV) oxides are poor electronic conductors, new methods developed to synthesize nanometer scale primary particles have achieved the higher rate capability needed for modern commercial applications. In this report, the anionic water stable titanium oxalate anion [TiO(C 2O 4) 2] 2- was isolated in high yield as the insoluble DABCO (1,4-diazabicyclo[2.2.2]octane) salt. Powder X-ray diffraction studies show that the titanium dioxide material isolated after annealing in air is initially amorphous, converts to N-doped anatase above 400 °C, then to rutile above 600 °C. Electrochemical studies indicate that the amorphous titanium dioxide phase within a carbon matrix has a stable cycling capacity of ∼350 mAh g -1. On crystallizing at 400 °C to a carbon-coated anatase the capacity drops to 210 mAh g -1, and finally upon carbon burn-off to 50 mAh g -1. Mixtures of the amorphous titanium dioxide and Li 4Ti 5O 12 showed a similar electrochemical profile and capacity to Li 4Ti 5O 12 but with the addition of a sloping region to the end of the discharge curve that could be advantageous for determining state-of-charge in systems using Li 4Ti 5O 12.

  2. Electrochemical formation and characterization of copolymers based on N-pyrrole derivatives.

    PubMed

    Okner, Regina; Domb, Abraham J; Mandler, Daniel

    2007-09-01

    Organic coatings based on N-(2-carboxyethyl)pyrrole (PPA) and a butyl ester of PPA (BuOPy) were deposited via electrochemical oxidation. The homo- and copolymers were electropolymerized on glassy carbon and stainless steel in acetonitrile using tetrabutylammonium tetrafluoraborate (Bu4NF4B) as the electrolyte. The mechanism of deposition on stainless steel was studied by chronoamperometry and by the tapping and phase angle imaging modes of atomic force microscopy. The electrochemical properties and growth of the films were investigated by cyclic voltammetry. The composition of the copolymers was determined by reflection-absorption Fourier transform infrared spectroscopy. We found that while the hydrophilic monomer PPA undergoes progressive nucleation followed by instantaneous growth the hydrophobic BuOPy nucleates instantaneously. The rate of BuOPy electropolymerization was higher than that of PPA, and the resulting film was thicker yet fluffier. Copolymer films were enriched by BuOPy as compared with the electropolymerization solution, which is attributed to the faster rate of electropolymerization of BuOPy than PPA.

  3. 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

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

    PubMed

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

    2015-05-06

    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(-1)electrode at power densities of ∼10 kW kg(-1)electrode for over 10,000 cycles.

  5. 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

  6. Superhydrophobic Surface Enhanced Raman Scattering Sensing using Janus Particle Arrays Realized by Site-Specific Electrochemical Growth

    PubMed Central

    Hricko, Patrick John; Huang, Po-Hsun; Li, Sixing; Zhao, Yanhui; Xie, Yuliang; Guo, Feng; Wang, Lin

    2014-01-01

    Site-specific electrochemical deposition is used to prepare polystyrene (PS)-Ag Janus particle arrays with superhydrophobic properties. The analyte molecules can be significantly enriched using the superhydrophobic property of the PS-Ag Janus particle array before SERS detections, enabling an extremely sensitive detection of molecules in a highly diluted solution (e.g., femtomolar level). This superhydrophobic surface enhanced Raman scattering sensing concept described here is of critical significance in biosensing and bioanalysis. Most importantly, the site-specific electrochemical growth method we developed here is a versatile approach that can be used to prepare Janus particle arrays with different properties for various applications. PMID:24748991

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. Understanding the mechanism of surface modification through enhanced thermal and electrochemical stabilities of N-doped graphene oxide

    NASA Astrophysics Data System (ADS)

    Mehetre, Shantilal S.; Maktedar, Shrikant S.; Singh, Man

    2016-03-01

    The kinetically active two dimensional surface of graphene oxide (GrO) plays an important role in understanding the chemistry of graphene. The GrO is comprises of carbon and oxygen while the f-(6-AIND) GrO contains nitrogen along with carbon and oxygen. The prominent thermal instability of GrO is widely explored. However, due to the synergistic impact of their constituting elements, the thermal and electrochemical stability of f-(6-AIND) GrO enhances after N-doping with nitrogen containing heterocycles like 6-Aminoindazole. Hence it is essential to probe the mutual impact of various functionalities present over the surface of GrO, to understand the mechanism of direct functionalization of GrO with thermal and electrochemical stabilities. Therefore, the decomposition kinetics of discrete atomic domains and their effect on thermal stability of f-(6-AIND) GrO was revealed with spectroscopic analysis and thermal assessment. Additionally, the mechanism of thermal transformation is precisely developed to demonstrate the impact of heat on weight loss due to the mass transfer. Likewise, the electrochemical properties can be well understood with the help of mechanism of electrochemical activity and cyclic voltammetry experiments. Also, the f-(6-AIND) GrO is confirmed with the help of various surface analysis techniques like FTIR, EDS, HR-XPS, HR-TEM, CV, SAED, TGA, DSC and UV-vis.

  12. Electrochemical and solid-state NMR studies on LiCoO 2 coated with Al 2O 3 derived from carboxylate-alumoxane

    NASA Astrophysics Data System (ADS)

    Fey, George T. K.; Kao, H. M.; Muralidharan, P.; Kumar, T. P.; Cho, Y. D.

    The surface of LiCoO 2 cathodes was coated with various wt.% of Al 2O 3 derived from methoxyethoxy acetate-alumoxane (MEA-alumoxane) by a mechano-thermal coating procedure, followed by calcination at 723 K in air for 10 h. The structure and morphology of the surface modified LiCoO 2 samples have been characterized with XRD, SEM, EDS, TEM, BET, XPS/ESCA and solid-state 27Al magic angle spinning (MAS) NMR techniques. The Al 2O 3 coating forms a thin layer on the surface of the core material with an average thickness of 20 nm. The corresponding 27Al MAS NMR spectrum basically exhibited the same characteristics as the spectrum for pristine Al 2O 3 derived from MEA-alumoxane, indicating that the local environment of aluminum atoms was not significantly changed at coating levels below 1 wt.%. This provides direct evidence that Al 2O 3 was on the surface of the core materials. The LiCoO 2 coated with 1 wt.% Al 2O 3 sustained continuous cycle stability 13 times longer than pristine LiCoO 2. A comparison of the electrochemical impedance behavior of the pristine and coated materials revealed that the failure of pristine cathode performance is associated with an increase in the particle-particle resistance upon continuous cycling. Coating improved the cathode performance by suppressing the characteristic structural phase transitions (hexagonal to monoclinic to hexagonal) that occur in pristine LiCoO 2 during the charge-discharge processes.

  13. Surface Characteristics and Electrochemical Impedance Investigation of Spark-Anodized Ti-6Al-4V Alloy

    NASA Astrophysics Data System (ADS)

    Garsivaz jazi, M. R.; Golozar, M. A.; Raeissi, K.; Fazel, M.

    2014-04-01

    In this study, the surface characteristic of oxide films on Ti-6Al-4V alloy formed by an anodic oxidation treatment in H2SO4/H3PO4 electrolyte at potentials higher than the breakdown voltage was evaluated. Morphology of the surface layers was studied by scanning electron microscope. The results indicated that the diameter of pores and porosity of oxide layer increase by increasing the anodizing voltage. The thickness measurement of the oxide layers showed a linear increase of thickness with increasing the anodizing voltage. The EDS analysis of oxide films formed in H2SO4/H3PO4 at potentials higher than breakdown voltage demonstrated precipitation of sulfur and phosphor elements from electrolyte into the oxide layer. X-ray diffraction was employed to exhibit the effect of anodizing voltage on the oxide layer structure. Roughness measurements of oxide layer showed that in spark anodizing, the Ra and Rz parameters would increase by increasing the anodizing voltage. The structure and Corrosion properties of oxide layers were studied using electrochemical impedance spectroscopy (EIS) techniques, in 0.9 wt.% NaCl solution. The obtained EIS spectra and their interpretation in terms of an equivalent circuit with the circuit elements indicated that the detailed impedance behavior is affected by three regions of the interface: the space charge region, the inner compact layer, and outer porous layer.

  14. Switching Transient Generation in Surface Interrogation Scanning Electrochemical Microscopy and Time-of-Flight Techniques.

    PubMed

    Ahn, Hyun S; Bard, Allen J

    2015-12-15

    In surface interrogation scanning electrochemical microscopy (SI-SECM), fine and accurate control of the delay time between substrate generation and tip interrogation (tdelay) is crucial because tdelay defines the decay time of the reactive intermediate. In previous applications of the SI-SECM, the resolution in the control of tdelay has been limited to several hundreds of milliseconds due to the slow switching of the bipotentiostat. In this work, we have improved the time resolution of tdelay control up to ca. 1 μs, enhancing the SI-SECM to be competitive in the time domain with the decay of many reactive intermediates. The rapid switching SI-SECM has been implemented in a substrate generation-tip collection time-of-flight (SG-TC TOF) experiment of a solution redox mediator, and the results obtained from the experiment exhibited good agreement with that obtained from digital simulation. The reaction rate constant of surface Co(IV) on oxygen-evolving catalyst film, which was inaccessible thus far due to the lack of tdelay control, has been measured by the rapid switching SI-SECM.

  15. Preparation and application of a novel electrochemical sensing material based on surface chemistry of polyhydroquinone.

    PubMed

    Dang, Xueping; Wang, Yingkai; Hu, Chengguo; Huang, Jianlin; Chen, Huaixia; Wang, Shengfu; Hu, Shengshui

    2014-07-01

    A new analogue of polydopamine (PDA), i.e., polyhydroquinone (PH2Q), was polymerized and its surface chemistry was studied by different ways of characterization. PH2Q was produced by the self-polymerization of H2Q mediated by dissolved oxygen, and the self-polymerization process was strongly dependent on the type and the pH value of the buffer solutions. PH2Q can not only achieve surface hydrophilization of different substrates like polyethylene terephthalate (PET) film, graphite strip, C12SH/Au and wax slice, but also possess several unique properties like reversible adsorption, good solubility and low cost. These properties made PH2Q an ideal polymeric modifier for the noncovalent functionalization of some nanomaterials. By simply grinding with PH2Q, pristine multi-walled carbon nanotubes (MWNTs) can be readily dispersed in water with high solubility and good stability. The resulting MWNT-PH2Q composite exhibited excellent electrochemical performance, which was employed for the simultaneous determination of dopamine (DA) and uric acid (UA).

  16. Electrochemical & osteoblast adhesion study of engineered TiO2 nanotubular surfaces on titanium alloys.

    PubMed

    Rahman, Zia Ur; Haider, Waseem; Pompa, Luis; Deen, K M

    2016-01-01

    TiO2 nanotubes were grafted on the surface of cpTi, Ti6Al4V and Ti6Al4V-ELI with the aim to provide a new podium for human pre-osteoblast cell (MC3T3) adhesion and proliferation. The surface morphology and chemistry of these alloys were examined with scanning electron microscopy and energy dispersive x-ray spectroscopy. TiO2 nanotubes were further characterized by cyclic potentiodynamic polarization tests and electrochemical impedance spectroscopy. The vertically aligned nanotubes were subjected to pre-osteoblast cell proliferation in order to better understand cell-material interaction. The study demonstrated that these cells interact differently with nanotubes of different titanium alloys. The significant acceleration in the growth rate of pre-osteoblast cell adhesion and proliferation is also witnessed. Additionally, the cytotoxicity of the leached metal ions was evaluated by using a tetrazolium-based bio-assay, MTS. Each group of data was operated for p<0.05, concluded one way ANOVA to investigate the significance difference.

  17. Sheath-Flow Microfluidic Approach for Combined Surface Enhanced Raman Scattering and Electrochemical Detection

    PubMed Central

    2015-01-01

    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. PMID:25815795

  18. Surface modification of β-Type titanium alloy by electrochemical potential pulse polarization

    NASA Astrophysics Data System (ADS)

    Fujimoto, Shinji; Raman, Vedarajan; Tsuchiya, Hiroaki

    2009-05-01

    In the present work, we report the formation of a porous oxide/hydroxide surface layer on the Ti-29Nb-13Ta-4.6Zr (TNTZ) alloy achieved by the combination of an alkali immersion and a potential pulse polarisation process. The alkali treatment has been employed for pure titanium to produce amorphous and porous layer prior to hydroxyapatite (HAp) growth. But, in the case of TNTZ, immersion in 5M NaOH at the open circuit potential (OCP) at 60°C for 24 hours, did not yield any uniform layer, instead a thick deposited layer with highly cracked one. The cracks were attributed to the growth of a tantalum enriched particulate. In order to avoid the crack formation, the electrochemical behaviour of the alloy and the pure alloying elements (Ti, Nb, Ta and Zr) was investigated to produce a uniform surface with the application of a square wave modulated potential pulse polarization, leading to the formation of a relatively uniform porous layer on the alloy.

  19. Surface functionalization of Bioglass-derived porous scaffolds.

    PubMed

    Chen, Qi-Zhi; Rezwan, Kurosch; Françon, Virginie; Armitage, David; Nazhat, Showan N; Jones, Francis H; Boccaccini, Aldo R

    2007-07-01

    Like standard tissue culture plates, tissue engineering scaffolds can be chemically treated to couple proteins without losing the conformation and thus biological function of the proteins; a process called surface functionalization. In this work, the surface of novel 45S5 Bioglass-derived foam-like scaffolds, which exhibit adequate mechanical stability and tailorable bioresorbability, have been modified by applying 3-aminopropyl-triethoxysilane. The efficiency and stability of the surface modification were satisfactorily and quantitatively assessed by X-ray photoemission spectroscopy. It was also found that treatment in buffered (pH 8) water solution at 80 degrees C for 4h, applied during the surface functionalization procedure, accelerated the bioreactive kinetics of the scaffolds, i.e. the transition of the relatively bioinert but mechanically competent crystalline structure of the struts to a biodegradable but mechanically weak amorphous network during immersion in simulated body fluid. Thus the aqueous heat treatment is confirmed to be an important factor that must be considered in the design of these Bioglass-derived glass-ceramic scaffolds. Possible mechanisms responsible for the accelerated bioreactivity are proposed.

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

    DOE PAGESBeta

    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). 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

  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. 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

  3. A mass spectrometric-derived cell surface protein atlas.

    PubMed

    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

  4. Electrochemical Surface Interrogation of a MoS2 Hydrogen-Evolving Catalyst: In Situ Determination of the Surface Hydride Coverage and the Hydrogen Evolution Kinetics.

    PubMed

    Ahn, Hyun S; Bard, Allen J

    2016-07-21

    The hydrogen evolution reaction (HER) on an electrodeposited a-MoS2 electrode was investigated by a surface-selective electrochemical titration technique by application of surface interrogation scanning electrochemical microscopy. In a mildly acidic (pH 4.6) environment, the saturated surface hydride coverage of MoS2 was determined to be 31%, much higher than that expected for a crystalline nanoparticle. The HER rate constant of a surface molybdenum atom was measured for the first time in situ to be 3.8 s(-1) at a 600 mV overpotential. At high Mo-H coverages, a change in the nature of the active sites was observed upon consumption of Mo-H by HER.

  5. Electrochemical Surface Interrogation of a MoS2 Hydrogen-Evolving Catalyst: In Situ Determination of the Surface Hydride Coverage and the Hydrogen Evolution Kinetics.

    PubMed

    Ahn, Hyun S; Bard, Allen J

    2016-07-21

    The hydrogen evolution reaction (HER) on an electrodeposited a-MoS2 electrode was investigated by a surface-selective electrochemical titration technique by application of surface interrogation scanning electrochemical microscopy. In a mildly acidic (pH 4.6) environment, the saturated surface hydride coverage of MoS2 was determined to be 31%, much higher than that expected for a crystalline nanoparticle. The HER rate constant of a surface molybdenum atom was measured for the first time in situ to be 3.8 s(-1) at a 600 mV overpotential. At high Mo-H coverages, a change in the nature of the active sites was observed upon consumption of Mo-H by HER. PMID:27383727

  6. 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.

  7. Facile preparation of carbon nanotube-conducting polymer network for sensitive electrochemical immunoassay of Hepatitis B surface antigen in serum.

    PubMed

    Hu, Yaogai; Zhao, Zhengyu; Wan, Qianqian

    2011-06-01

    A novel electrochemical immunosensor built on three dimensional carbon nanotube-conducting polymer (CNT-CP) network is reported for detection of Hepatitis B surface antigen (HBsAg) in human serum. The CNT-CP network is prepared by drop-drying of CNT solution on glassy carbon electrode, followed by electrochemical polymerization of poly (pyrrole propionic acid) (pPPA) film to crosslink and stabilize the CNTs, wherein the CNTs form the backbone of the network, and offer great specific surface areas for antibody attachment, and confer good conductivity for electrochemical detection, while the conducting film integrates the carbon nanotubes into a stable network due to its self-limiting growth behavior and provides abundant carboxyl groups for covalent immobilization of probe proteins. As a unique matrix, the CNT-CP network enables sensitive electrochemical detection of HBsAg biomarker by using alkaline phosphatase (ALP)-conjugated secondary antibodies under sandwich format coupling with the ALP substrate solution, p-aminophenyl phosphate (PAPP), reaching a detection limit of 0.01ng/mL with a dynamic range of 5 orders of magnitude.

  8. 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.

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

    PubMed Central

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

    2011-01-01

    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. PMID:20880853

  10. Influence of surface acoustic waves induced acoustic streaming on the kinetics of electrochemical reactions

    NASA Astrophysics Data System (ADS)

    Tietze, Sabrina; Schlemmer, Josefine; Lindner, Gerhard

    2013-12-01

    The kinetics of electrochemical reactions is controlled by diffusion processes of charge carriers across a boundary layer between the electrode and the electrolyte, which result in a shielding of the electric field inside the electrolyte and a concentration gradient across this boundary layer. In accumulators the diffusion rate determines the rather long time needed for charging, which is a major drawback for electric mobility. This diffusion boundary can be removed by acoustic streaming in the electrolyte induced by surface acoustic waves propagating of the electrode, which results in an increase of the charging current and thus in a reduction of the time needed for charging. For a quantitative study of the influence of acoustic streaming on the charge transport an electropolishing cell with vertically oriented copper electrodes and diluted H3PO4-Propanol electrolytes were used. Lamb waves with various excitation frequencies were exited on the anode with different piezoelectric transducers, which induced acoustic streaming in the overlaying electrolytic liquid. An increase of the polishing current of up to approximately 100 % has been obtained with such a set-up.

  11. Contactless surface conductivity mapping of graphene oxide thin films deposited on glass with scanning electrochemical microscopy.

    PubMed

    Azevedo, Joel; Bourdillon, Céline; Derycke, Vincent; Campidelli, Stéphane; Lefrou, Christine; Cornut, Renaud

    2013-02-01

    The present article introduces a rapid, very sensitive, contactless method to measure the local surface conductivity with Scanning Electrochemical Microscopy (SECM) and obtain conductivity maps of heterogeneous substrates. It is demonstrated through the study of Graphene Oxide (GO) thin films deposited on glass. The adopted substrate preparation method leads to conductivity disparities randomly distributed over approximately 100 μm large zones. Data interpretation is based on an equation system with the dimensionless conductivity as the only unknown parameter. A detailed prospection provides a consistent theoretical framework for the reliable quantification of the conductivity of GO with SECM. Finally, an analytical approximation of the conductivity as a function of the feedback current is proposed, making any further interpretation procedure straightforward, as it does not require iterative numerical simulations any more. The present work thus provides not only valuable information on the kinetics of GO reduction in mild conditions but also a general and simplified interpretation framework that can be extended to the quantitative conductivity mapping of other types of substrates. PMID:23259661

  12. 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.

  13. Electrochemical preparation of silver and gold nanoparticles: Characterization by confocal and surface enhanced Raman microscopy

    NASA Astrophysics Data System (ADS)

    Plieth, W.; Dietz, H.; Anders, A.; Sandmann, G.; Meixner, A.; Weber, M.; Kneppe, H.

    2005-12-01

    Localized silver and gold nanoparticles, electrochemically prepared by means of the double-pulse technique, were investigated with respect to their optical and spectroscopic properties by scanning confocal microscopy combined with surface enhanced Raman spectroscopy (SERS) and subsequent comparison with the local image of scanning electron microscopy (SEM). Analogous to the silver cluster preparation technique, controlled electrodeposition of gold nanoparticles was demonstrated, varying size from 10 to 500 nm and particle density. The maximum SERS enhancement factors found in the measurements were: (i) 10 10 for silver particles and (ii) 10 8 for gold particles. The optical and spectroscopic data of the local nanoparticle structures investigated showed that SERS is a local phenomenon, because (i) only few particles are Raman active particles, (ii) strongest enhancements in SERS are obtained from particle agglomerates, (iii) typically the Raman radiation is emitted from irregular structures like the necks between two or more particles agglomerated. In the investigated range from 10 to 500 nm no significant influence of the particle size was observed.

  14. Surface morphology and electrochemical characterization of electrodeposited Ni-Mo nanocomposites as cathodes for hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Elhachmi Guettaf, Temam; Hachemi Ben, Temam; Said, Benramache

    2015-10-01

    In this work, we study the influences of current density on surface morphology and electrochemical characterization of electrodeposited Ni-Mo. The Ni-Mo composite coatings are deposited on pretreated copper substrates by electrolytic deposition. The Ni-Mo solution is taken from nickel sulfate fluid and ammonium heptamolybdate with 10 g/l. The Ni-Mo composite coatings are deposited at a temperature of 303 K with an applied current density of jdep = 10 A/dm2-30 A/dm2. We find that the corrosion resistance is improved by incorporating Mo particles into Ni matrix in 0.6-M NaCl solution. From the potentiodynamic polarization curve of electrodeposited Ni-Mo it is confirmed that the corrosion resistance decreases with increasing applied current density. The x-ray diffraction (XRD) analyses of Ni-Mo coatings indicate three phases of MoNi4, Mo1.24Ni0.76, and Ni3Mo phases crystallites of nickel and molybdenum. The scanning electronic microscopy (SEM) tests indicate that Ni-Mo coatings present cracks and pores.

  15. Rapid fabrication of SERS substrate and superhydrophobic surface with different micro/nano-structures by electrochemical shaping of smooth Cu surface

    NASA Astrophysics Data System (ADS)

    Guo, Manman; Liu, Meili; Zhao, Wei; Xia, Yue; Huang, Wei; Li, Zelin

    2015-10-01

    Direct electrochemical shaping of metal surfaces into micro/nano-structures with desired functions is interesting and attractive. In this work, we employed square wave potential pulses (SWPP) to shape a smooth Cu surface into micro/nano-structures efficiently in a blank H2SO4 solution. Delightedly, we obtained Cu sub-micrometric islands on the surface with very strong surface enhanced Raman scattering (SERS) effect in 5 s, and fabricated a coral-like micro/nano-structured copper film with superhydrophobicity in 40 s. This method is green, facile, fast, and easy to control.

  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. Neurocognitive derivation of protein surface property from protein aggregate parameters

    PubMed Central

    Mishra, Hrishikesh; Lahiri, Tapobrata

    2011-01-01

    Current work targeted to predicate parametric relationship between aggregate and individual property of a protein. In this approach, we considered individual property of a protein as its Surface Roughness Index (SRI) which was shown to have potential to classify SCOP protein families. The bulk property was however considered as Intensity Level based Multi-fractal Dimension (ILMFD) of ordinary microscopic images of heat denatured protein aggregates which was known to have potential to serve as protein marker. The protocol used multiple ILMFD inputs obtained for a protein to produce a set of mapped outputs as possible SRI candidates. The outputs were further clustered and largest cluster centre after normalization was found to be a close approximation of expected SRI that was calculated from known PDB structure. The outcome showed that faster derivation of individual protein’s surface property might be possible using its bulk form, heat denatured aggregates. PMID:21572883

  18. Mechanical and surface analysis of stilbazolium tosylate derivative crystals

    NASA Astrophysics Data System (ADS)

    Kalainathan, S.; Jagannathan, K.

    2008-04-01

    The highly efficient nonlinear optical (NLO) crystals, 4-dimethylamino- N-methyl 4 stilbazolium tosylate (DAST) crystals, have been grown by the slope nucleation technique (SNT) and the new derivative in the same family, 4-ethoxy benzaldehyde- N-methyl 4 stilbazolium tosylate (EBST) crystals by slow evaporation technique. In this present work the mechanical, dielectric studies and surface analysis of EBST and DAST were compared. The Meyer's index number ( n), fracture toughness and brittle index were calculated using Vicker's microhardness number. Young's modulus was calculated using the Knoop hardness value. The surfaces of the grown crystals were analyzed with etching. The etching was done using methanol as solvent. The dc conductivity was calculated from the dielectric study by the cole-cole plot method. The dielectric constant and dielectric loss were found to decreased when the frequency increased.

  19. Electrochemical functionalization of carbon surfaces by aromatic azide or alkyne molecules: a versatile platform for click chemistry.

    PubMed

    Evrard, David; Lambert, François; Policar, Clotilde; Balland, Véronique; Limoges, Benoît

    2008-01-01

    The electrochemical reduction of phenylazide or phenylacetylene diazonium salts leads to the grafting of azido or ethynyl groups onto the surface of carbon electrodes. In the presence of copper(I) catalyst, these azide- or alkyne-modified surfaces react efficiently and rapidly with compounds bearing an acetylene or azide function, thus forming a covalent 1,2,3-triazole linkage by means of click chemistry. This was illustrated with the surface coupling of ferrocenes functionalized with an ethynyl or azido group and the biomolecule biotin terminated by an acetylene group.

  20. 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.

  1. 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.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

    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.

  4. Optimization of electrochemical aptamer-based sensors via optimization of probe packing density and surface chemistry.

    PubMed

    White, Ryan J; Phares, Noelle; Lubin, Arica A; Xiao, Yi; Plaxco, Kevin W

    2008-09-16

    Electrochemical, aptamer-based (E-AB) sensors, which are comprised of an electrode modified with surface immobilized, redox-tagged DNA aptamers, have emerged as a promising new biosensor platform. In order to further improve this technology we have systematically studied the effects of probe (aptamer) packing density, the AC frequency used to interrogate the sensor, and the nature of the self-assembled monolayer (SAM) used to passivate the electrode on the performance of representative E-AB sensors directed against the small molecule cocaine and the protein thrombin. We find that, by controlling the concentration of aptamer employed during sensor fabrication, we can control the density of probe DNA molecules on the electrode surface over an order of magnitude range. Over this range, the gain of the cocaine sensor varies from 60% to 200%, with maximum gain observed near the lowest probe densities. In contrast, over a similar range, the signal change of the thrombin sensor varies from 16% to 42% and optimal signaling is observed at intermediate densities. Above cut-offs at low hertz frequencies, neither sensor displays any significant dependence on the frequency of the alternating potential employed in their interrogation. Finally, we find that E-AB signal gain is sensitive to the nature of the alkanethiol SAM employed to passivate the interrogating electrode; while thinner SAMs lead to higher absolute sensor currents, reducing the length of the SAM from 6-carbons to 2-carbons reduces the observed signal gain of our cocaine sensor 10-fold. We demonstrate that fabrication and operational parameters can be varied to achieve optimal sensor performance and that these can serve as a basic outline for future sensor fabrication.

  5. 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.

  6. 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.

  7. Electrochemical behaviour and surface characterisation of Zr exposed to an SBF solution containing glycine, in view of dental implant applications.

    PubMed

    Bozzini, Benedetto; Carlino, Paolo; Mele, Claudio

    2011-01-01

    Zr and Ti alloys are extensively used in the biomedical field owing to their optimal mechanical properties and excellent corrosion resistance. Fully ceramic implants based on zirconia are appealing with respect to the traditional Ti-based metallic ones for several reasons, such as: (i) improved aesthetic impact, (ii) better biocompatibility and (iii) better osteointegration. Nevertheless, fully ceramic implants exhibit serious mechanical and clinical drawbacks, chiefly brittleness and impossibility of post-implant position adjustments. In this paper we propose the novel approach of using a metal-based system, consisting of metallic Zr, for the bulk of the implant and an electrochemically grown zirconia coating, ensuring contact of the ceramic with the biological environment and isolation from the underlying metal. This solution combines the outstanding mechanical properties of the metal in the bulk with the optimal biochemical properties exclusively where they are needed: at the surface. The present paper-focussed on the electrochemical behaviour of the proposed system at the implant-wound and implant-growing bone interface-reports a time-dependent electrochemical corrosion study of zirconia-coated zirconium, performed in the following ways: (i) exposure and measurements in SBF (simulating the inorganic part of human plasma, relevant to wound chemistry), (ii) exposure and measurements in SBF with added glycine (the simplest, ubiquitous amino acid found in proteins), (iii) exposure in SBF with added glycine and measurements in SBF. Electrochemical impedance spectra were measured and interpreted with the equivalent-circuit approach, yielding estimates of the time-variation of the oxide film thickness and resistance were estimated. FT-IR, Surface Raman and VIS reflectance spectroscopies were used to characterise the surface before and after the exposure to SBF solutions. Spectroelectrochemical measurements revealed an higher corrosion resistance of the oxide films

  8. Electrochemical oxidation of ampicillin antibiotic at boron-doped diamond electrodes and process optimization using response surface methodology.

    PubMed

    Körbahti, Bahadır K; Taşyürek, Selin

    2015-03-01

    Electrochemical oxidation and process optimization of ampicillin antibiotic at boron-doped diamond electrodes (BDD) were investigated in a batch electrochemical reactor. The influence of operating parameters, such as ampicillin concentration, electrolyte concentration, current density, and reaction temperature, on ampicillin removal, COD removal, and energy consumption was analyzed in order to optimize the electrochemical oxidation process under specified cost-driven constraints using response surface methodology. Quadratic models for the responses satisfied the assumptions of the analysis of variance well according to normal probability, studentized residuals, and outlier t residual plots. Residual plots followed a normal distribution, and outlier t values indicated that the approximations of the fitted models to the quadratic response surfaces were very good. Optimum operating conditions were determined at 618 mg/L ampicillin concentration, 3.6 g/L electrolyte concentration, 13.4 mA/cm(2) current density, and 36 °C reaction temperature. Under response surface optimized conditions, ampicillin removal, COD removal, and energy consumption were obtained as 97.1 %, 92.5 %, and 71.7 kWh/kg CODr, respectively.

  9. 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.

  10. Electrochemical oxidation of ampicillin antibiotic at boron-doped diamond electrodes and process optimization using response surface methodology.

    PubMed

    Körbahti, Bahadır K; Taşyürek, Selin

    2015-03-01

    Electrochemical oxidation and process optimization of ampicillin antibiotic at boron-doped diamond electrodes (BDD) were investigated in a batch electrochemical reactor. The influence of operating parameters, such as ampicillin concentration, electrolyte concentration, current density, and reaction temperature, on ampicillin removal, COD removal, and energy consumption was analyzed in order to optimize the electrochemical oxidation process under specified cost-driven constraints using response surface methodology. Quadratic models for the responses satisfied the assumptions of the analysis of variance well according to normal probability, studentized residuals, and outlier t residual plots. Residual plots followed a normal distribution, and outlier t values indicated that the approximations of the fitted models to the quadratic response surfaces were very good. Optimum operating conditions were determined at 618 mg/L ampicillin concentration, 3.6 g/L electrolyte concentration, 13.4 mA/cm(2) current density, and 36 °C reaction temperature. Under response surface optimized conditions, ampicillin removal, COD removal, and energy consumption were obtained as 97.1 %, 92.5 %, and 71.7 kWh/kg CODr, respectively. PMID:24906830

  11. Effect of ammonium-salt solutions on the surface properties of carbon fibers in electrochemical anodic oxidation

    NASA Astrophysics Data System (ADS)

    Qian, Xin; Wang, Xuefei; Ouyang, Qin; Chen, Yousi; Yan, Qing

    2012-10-01

    The surfaces of polyacrylonitrile-based carbon fibers were treated by an electrochemical anodic method. Three different kinds of ammonium-salt solutions namely NH4HCO3, (NH4)2CO3 and (NH4)3PO4 were respectively chosen as the electrolytes. The effect of these electrolytes on the surface structure was studied by scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The results showed that longitudinal grooves on the fiber surface became more well-defined and much deeper after surface treatment, and the root mean square roughness (RMS) of carbon fiber surface increased from 4.6 nm for untreated fibers to 13.5 nm for treated fibers in (NH4)3PO4 electrolytes. The concentration of oxygen and nitrogen atomic on the fiber surface increased after surface treatment. The tensile strength of oxidized fibers had an obvious decrease, whereas the interlaminar shear strength (ILSS) value of corresponding carbon fiber reinforced polymers (CFRPs) increased in a large extent. The intensity of oxidative reaction varied with the change of ammonium-salt solutions and electrochemical oxidation in (NH4)3PO4 electrolyte was of the most violence. The corresponding mechanism was also discussed and the result showed that the higher the concentration of OH- ions in the electrolytes, the violent the oxidative reaction happened.

  12. 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.

  13. 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

  14. A study of the effects of phosphates on copper corrosion in drinking water: Copper release, electrochemical, and surface analysis approach

    NASA Astrophysics Data System (ADS)

    Kang, Young C.

    The following work is the study to evaluate the impact of corrosion inhibitors on the copper metal in drinking water and to investigate the corrosion mechanism in the presence and absence of inhibitors. Electrochemical experiments were conducted to understand the effect of specific corrosion inhibitors in synthetic drinking water which was prepared with controlled specific water quality parameters. Water chemistry was studied by Inductively Coupled Plasma--Atomic Emission Spectroscopy (ICP--AES) to investigate the copper leaching rate with time. Surface morphology, crystallinity of corrosion products, copper oxidation status, and surface composition were characterized by various solid surface analysis methods, such as Scanning Electron Microscopy/Energy--Dispersive Spectrometry (SEM/EDS), Grazing-Incidence-angle X-ray Diffraction (GIXRD), X-ray Photoelectron Spectroscopy (XPS), and Time-of-Flight Secondary Ions Mass Spectrometry (ToF-SIMS). The purpose of the first set of experiments was to test various electrochemical techniques for copper corrosion for short term before studying a long term loop system. Surface analysis techniques were carried out to identify and study the corrosion products that form on the fresh copper metal surface when copper coupons were exposed to test solutions for 2 days of experiments time. The second phase of experiments was conducted with a copper pipe loop system in a synthetic tap water over an extended period of time, i.e., 4 months. Copper release and electrochemically measured corrosion activity profiles were monitored carefully with and without corrosion inhibitor, polyphosphate. A correlation between the copper released into the solution and the electrochemically measured corrosion activities was also attempted. To investigate corrosion products on the copper pipe samples, various surface analysis techniques were applied in this study. Especially, static mass spectra acquisition and element distribution mapping were carried out

  15. 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}.

  16. Sealing of pores in sol-gel-derived tritium permeation barrier coating by electrochemical technique

    NASA Astrophysics Data System (ADS)

    Zhang, Kun; Hatano, Yuji

    2011-10-01

    An electrolytic deposition technique was applied to seal open pores in sol-gel derived ZrO 2 coating and to improve barrier effects against permeation of hydrogen isotopes. Disk-type specimens of type 430 ferritic stainless steel were first covered by thin ZrO 2 films (50 nm) with a conventional sol-gel technique. Then, pores in the ZrO 2 film was sealed with ZrO 2 or Al 2O 3 by cathodic processes in ethanol solution of Zr or Al nitrate and subsequent heat treatments in air. The permeation rate of hydrogen was measured at 300-600 °C. The sol-gel derived ZrO 2 coatings showed only limited barrier effects; the permeation reduction factor (PRF) was about 6-800. Nevertheless, the treatments by electrolytic deposition technique resulted in considerable improvement in the barrier effects, especially at high temperature region (>500 °C), and the PRF increased to 100-1000.

  17. 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.

  18. 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.

  19. 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

  20. Liquid organic hydrogen carriers: surface science studies of carbazole derivatives.

    PubMed

    Papp, Christian; Wasserscheid, Peter; Libuda, Jörg; Steinrück, Hans-Peter

    2014-10-01

    We review recent results towards a molecular understanding of the adsorption and dehydrogenation of carbazole-derived liquid organic hydrogen carriers on platinum and palladium single crystals and on Al2 O3 -supported Pt and Pd nanoparticles. By combining synchrotron-based high-resolution X-ray photoelectron spectroscopy, infrared reflection-absorption spectroscopy, advanced molecular beam methods and temperature-programmed desorption spectroscopy, detailed insights into the reaction mechanism are obtained. On Pt(111), dehydrogenation of perhydro-N-ethylcarbazole, H12 -NEC, starts with activation of the hydrogen atoms at the pyrrole unit, yielding H8 -NEC as the first stable reaction intermediate at ∼340 K, followed by further dehydrogenation to NEC at ∼380 K. Above 390 K, dealkylation starts, yielding carbazole as an undesired byproduct. On small supported Pt particles, the dealkylation sets in at lower temperatures, due to the higher reactivity of low-coordinated sites, while on larger particles with (111) facets a reactivity as on the flat surface is observed. Carbazole derivatives with ethyl, propyl and butyl chains show an overall very similar reactivity, both on Pt(111) and on Pt nanoparticles. When comparing the dealkylation behavior of H12 -NEC on Pt(111) and Pt nanoparticles to that on Pd(111) and Pd nanoparticles, we find a higher reactivity for the Pd systems.

  1. 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.

  2. 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

  3. 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

  4. Electrochemical functionalization of gold and silicon surfaces by a maleimide group as a biosensor for immunological application.

    PubMed

    Zhang, Xin; Tretjakov, Aleksei; Hovestaedt, Marc; Sun, Guoguang; Syritski, Vitali; Reut, Jekaterina; Volkmer, Rudolf; Hinrichs, Karsten; Rappich, Joerg

    2013-03-01

    In the present study we investigated the preparation of biofunctionalized surfaces using the direct electrochemical grafting of maleimidophenyl molecules with subsequent covalent immobilization of specific peptide to detect target antibody, thereby extending the application of the biosensing systems towards immunodiagnostics. Para-maleimidophenyl (p-MP) functional groups were electrochemically grafted on gold and silicon surfaces from solutions of the corresponding diazonium salt. A specially synthesized peptide modified with cysteine (Cys-peptide) was then immobilized on the p-MP grafted substrates by cross-linking between the maleimide groups and the sulfhydryl group of the cysteine residues. Accordingly, the Cys-peptide worked as an antigen that was able to bind specifically the target antibody (anti-GST antibody), while it was non-sensitive to a negative contrast antibody (i.e. anti-Flag β). The immobilization of both specific and non-specific antibodies on the Cys-peptide-modified surfaces was monitored by infrared spectroscopic ellipsometry, a quartz crystal microbalance integrated in flow injection analysis system and potentiometric response. The results obtained clearly demonstrated that the direct modification of a surface with maleimidophenyl provides a very simple and reliable way of preparing biofunctionalized surfaces suitable for the construction of immunological biosensors.

  5. 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.

  6. 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. PMID:26893092

  7. Electrochemical discrimination of phthalic acid among three phthalic acid isomers based on an N-butylaminomethyl-ferrocene derivative.

    PubMed

    Yoon, Jisoo; Jadhav, Jyoti Ramesh; Kim, Jun Myung; Cheong, Minserk; Kim, Hong-Seok; Kim, Joohoon

    2014-07-21

    A chemosensor compound (1) consisting of a central ferrocene with two butylaminomethyl arms showed unexpected facile electrochemical oxidation of the secondary amines in proximity to the ferrocene, which was utilized for electrochemical discrimination of phthalic acid selectively over two other isomers, isophthalic acid and terephthalic acid.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    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.

  9. 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.

  10. 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

  11. Pratt and Whitney ESCORT derivative for mars surface power

    SciTech Connect

    Feller, Gerald J.; Joyner, Russell

    1999-01-22

    The purpose of this paper is to address the applicability of a common reactor system design from the Pratt and 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 mx4.5 mx4.4 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

  12. 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

  13. 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…

  14. 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.

  15. 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

  16. Microscopically derived potential energy surfaces from mostly structural considerations

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    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.

  17. Improved electrochemical stability at the surface of La(0.8)Sr(0.2)CoO3 achieved by surface chemical modification.

    PubMed

    Tsvetkov, Nikolai; Lu, Qiyang; Yildiz, Bilge

    2015-01-01

    The degradation of the surface chemistry on perovskite (ABO3) oxides is a critical issue for their performance in energy conversion systems such as solid oxide fuel/electrolysis cells and in splitting of H2O and CO2 to produce fuels. This degradation is typically in the form of segregation and phase separation of dopant cations from the A-site, driven by elastic and electrostatic energy minimization and kinetic demixing. In this study, deposition of Ti at the surface was found to hinder the dopant segregation and the corresponding electrochemical degradation on a promising SOFC cathode material, La(0.8)Sr(0.2)CoO3 (LSC). The surface of the LSC films was modified by Ti (denoted as LSC-T) deposited from a TiCl4 solution. The LSC and LSC-T thin films were investigated by electrochemical impedance spectroscopy, nano-probe Auger electron spectroscopy, and X-ray photoelectron spectroscopy (XPS), upon annealing at 420-530 °C in air up to about 90 hours. The oxygen exchange coefficient, k(q), on LSC-T cathodes was found to be up to 8 times higher than that on LSC cathodes at 530 °C and retained its stability. Sr-rich insulating particles formed at the surface of the annealed LSC and LSC-T films, but with significantly less coverage of such particles on the LSC-T. From this result, it appears that modification of the LSC surface with Ti reduces the segregation of the blocking Sr-rich particles at the surface, and a larger area on LSC surface (with a higher Sr doping level in the lattice) is available for the oxygen reduction reaction. The stabilization of the LSC surface through Ti-deposition can open a new route for designing surface modifications on perovskite oxide electrodes for high temperature electro- and thermo-chemical applications. PMID:26227310

  18. An electrochemical and surface analysis study of the influence of phosphorus on the corrosion of iron in calcium nitrate

    SciTech Connect

    Windisch, C.F. Jr.; Baer, D.R.; Jones, R.H.; Engelhard, M.H.

    1990-10-01

    Intergranular stress corrosion cracking (IGSCC) of metallic alloys including iron is strongly influenced by the presence of grain boundary impurities such as phosphorus. In this study to determine how phosphorus affects the corrosion of iron, electrochemical polarization methods were used in conjunction with surface analyses employing ultra-high vacuum transfer. Specifically, these methods were used to examine the corrosion of iron, iron/phosphorus alloys, and iron implanted with phosphorus in deaerated 55 wt % Ca(NO{sub 3}){sub 2} solutions at 60{degree}C. 18 refs., 13 figs., 1 tab.

  19. 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

  20. 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.

  1. 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

    2016-01-01

    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

  2. Electrochemically modified carbon and chromium surfaces for AFM imaging of double-strand DNA interaction with transposase protein.

    PubMed

    Esnault, Charles; Chénais, Benoît; Casse, Nathalie; Delorme, Nicolas; Louarn, Guy; Pilard, Jean-François

    2013-02-01

    Carbon and chromium surfaces were modified by electrochemical reduction of a diazonium salt formed in situ from the sulfanilic acid. The organic layer formed was activated by phosphorus pentachloride (PCl(5)) to form a benzene sulfonil chloride (Ar-SO(2)Cl). An electrochemical study of the blocking effect and the activity of this surface was carried out on a carbon electrode. The chromium surface study was completed by X-ray photoelectron spectroscopy and atomic force microscopy to characterize the formation of a compact monolayer (0.8 nm height and roughness 0.2-0.3 nm). The compactness and the activity of this organic monolayer allowed us to affix a length dsDNA with the aim of analyzing the formation of a complex between dsDNA and a protein. The interaction of a transposase protein with its target dsDNA was investigated. The direct imaging of the nucleoproteic complex considered herein gives new insights in the comprehension of transposase-DNA interaction in agreement with biochemical data.

  3. Research on the structure-surface adsorptive activity relationships of triazolyl glycolipid derivatives for mild steel in HCl.

    PubMed

    Zhang, Hai-Lin; He, Xiao-Peng; Deng, Qiong; Long, Yi-Tao; Chen, Guo-Rong; Chen, Kaixian

    2012-06-01

    Triazolyl glycolipid derivatives constructed via Cu(I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition reaction (Cue-AAC) represent a new range of carbohydrate-based scaffolds for use in many fields of the chemical research. Here the surface adsorptive ability of series of our previously prepared C1- or C6-triazole linked gluco- and galactolipid derivatives for mild steel in 1 M HCl was studied via electrochemical impedance spectroscopy (EIS). Results indicated that these monosaccharide-fatty acid conjugates are weak inhibitors against HCl corrosion for mild steel. Moreover, some newly synthesized triazolyl disaccharide (maltose)-fatty alcohol conjugates failed to display enhanced activity, meaning that the structural enlargement of the sugar moiety does not favor the iron surface adsorption. However, a bis-triazolyl glycolipid derivative, which was realized by introducing a benzenesulfonamide group via Cue-AAC to the C6-position of a C1-triazolyl glucolipid analog, eventually showed significantly improved adsorptive potency compared to that of its former counterparts. The corrosion inhibitive modality of this compound for mild steel in HCl was subsequently studied via potentiodynamic polarization and thermodynamic calculations.

  4. 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.

  5. Compressive Strength of Cometary Surfaces Derived from Radar Observations

    NASA Astrophysics Data System (ADS)

    ElShafie, A.; Heggy, E.

    2014-12-01

    Landing on a comet nucleus and probing it, mechanically using harpoons, penetrometers and drills, and electromagnetically using low frequency radar waves is a complex task that will be tackled by the Rosetta mission for Comet 67P/Churyumov-Gerasimenko. The mechanical properties (i.e. density, porosity and compressive strength) and the electrical properties (i.e. the real and imaginary parts of the dielectric constant) of the comet nucleus, constrain both the mechanical and electromagnetic probing capabilities of Rosetta, as well as the choice of landing site, the safety of the landing, and subsurface data interpretation. During landing, the sounding radar data that will be collected by Rosetta's CONSERT experiment can be used to probe the comet's upper regolith layer by assessing its dielectric properties, which are then inverted to retrieve the surface mechanical properties. These observations can help characterize the mechanical properties of the landing site, which will optimize the operation of the anchor system. In this effort, we correlate the mechanical and electrical properties of cometary analogs to each other, and derive an empirical model that can be used to retrieve density, porosity and compressive strength from the dielectric properties of the upper regolith inverted from CONSERT observations during the landing phase. In our approach we consider snow as a viable cometary material analog due to its low density and its porous nature. Therefore, we used the compressive strength and dielectric constant measurements conducted on snow at a temperature of 250 K and a density range of 0.4-0.9 g/cm3 in order to investigate the relation between compressive strength and dielectric constant under cometary-relevant density range. Our results suggest that compressive strength increases linearly as function of the dielectric constant over the observed density range mentioned above. The minimum and maximum compressive strength of 0.5 and 4.5 MPa corresponded to a

  6. Electroendocytosis Is Driven by the Binding of Electrochemically Produced Protons to the Cell’s Surface

    PubMed Central

    Ben-Dov, Nadav; Rozman Grinberg, Inna; Korenstein, Rafi

    2012-01-01

    Electroendocytosis involves the exposure of cells to pulsed low electric field and is emerging as a complementary method to electroporation for the incorporation of macromolecules into cells. The present study explores the underlying mechanism of electroendocytosis and its dependence on electrochemical byproducts formed at the electrode interface. Cell suspensions were exposed to pulsed low electric field in a partitioned device where cells are spatially restricted relative to the electrodes. The cellular uptake of dextran-FITC was analyzed by flow cytometery and visualized by confocal microscopy. We first show that uptake occurs only in cells adjacent to the anode. The enhanced uptake near the anode is found to depend on electric current density rather than on electric field strength, in the range of 5 to 65 V/cm. Electrochemically produced oxidative species that impose intracellular oxidative stress, do not play any role in the stimulated uptake. An inverse dependence is found between electrically induced uptake and the solution’s buffer capacity. Electroendocytosis can be mimicked by chemically acidifying the extracellular solution which promotes the enhanced uptake of dextran polymers and the uptake of plasmid DNA. Electrochemical production of protons at the anode interface is responsible for inducing uptake of macromolecules into cells exposed to a pulsed low electric field. Expanding the understanding of the mechanism involved in electric fields induced drug-delivery into cells, is expected to contribute to clinical therapy applications in the future. PMID:23209699

  7. Surface-induced intramolecular electron transfer in multi-centre redox metalloproteins: the di-haem protein cytochrome c4 in homogeneous solution and at electrochemical surfaces

    NASA Astrophysics Data System (ADS)

    Chi, Qijin; Zhang, Jingdong; Jensen, Palle S.; Nazmudtinov, Renat R.; Ulstrup, Jens

    2008-09-01

    Intramolecular electron transfer (ET) between transition metal centres is a core feature of biological ET and redox enzyme function. The number of microscopic redox potentials and ET rate constants is, however, mostly prohibitive for experimental mapping, but two-centre proteins offer simple enough communication networks for complete mapping to be within reach. At the same time, multi-centre redox proteins operate in a membrane environment where conformational dynamics and ET patterns are quite different from the conditions in a homogeneous solution. The bacterial respiratory di-haem protein Pseudomonas stutzeri cytochrome c4 offers a prototype target for environmental gating of intra-haem ET. ET between P. stutzeri cyt c4 and small molecular reaction partners in solution appears completely dominated by intermolecular ET of each haem group/protein domain, with no competing intra-haem ET, for which accompanying propionate-mediated proton transfer is a further barrier. The protein can, however, be immobilized on single-crystal, modified Au(111) electrode surfaces with either the low-potential N terminal or the high-potential C terminal domain facing the surface, clearly with fast intramolecular ET as a key feature in the electrochemical two-ET process. This dual behaviour suggests a pattern for multi-centre redox metalloprotein function. In a homogeneous solution, which is not the natural environment of cyt c4, the two haem group domains operate largely independently with conformations prohibitive for intramolecular ET. Binding to a membrane or electrochemical surface, however, triggers conformational opening of intramolecular ET channels. The haem group orientation in P. stutzeri cyt c4 is finally noted to offer a case for orientation dependent electronic rectification between a substrate and a tip in electrochemical in situ scanning tunnelling microscopy or nanoscale electrode configurations.

  8. 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.

  9. 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. PMID:27267938

  10. 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.

  11. Assembling Paramagnetic Ceruloplasmin at Electrode Surfaces Covered with Ferromagnetic Nanoparticles. Scanning Electrochemical Microscopy in the Presence of a Magnetic Field.

    PubMed

    Matysiak, Edyta; Botz, Alexander J R; Clausmeyer, Jan; Wagner, Barbara; Schuhmann, Wolfgang; Stojek, Zbigniew; Nowicka, Anna M

    2015-07-28

    Adsorption of ceruloplasmin (Cp) at a gold electrode modified with ferromagnetic iron nanoparticles encapsulated in carbon (Fe@C Nps) leads to a successful immobilization of the enzyme in its electroactive form. The proper placement of Cp at the electrode surface on top of the nanocapsules containing an iron core allowed a preorientation of the enzyme, hence allowing direct electron transfer between the electrode and the enzyme. Laser ablation coupled with inductively coupled plasma mass spectrometry indicated that Cp was predominantly located at the paramagnetic nanoparticles. Scanning electrochemical microscopy measurements in the sample-generation/tip-collection mode proved that Cp was ferrooxidative inactive if it was immobilized on the bare gold surface and reached the highest activity if it was adsorbed on Fe@C Nps in the presence of a magnetic field.

  12. High-efficiency electrochemical hydrogen evolution based on surface autocatalytic effect of ultrathin 3C-SiC nanocrystals.

    PubMed

    He, Chengyu; Wu, Xinglong; Shen, Jiancang; Chu, Paul K

    2012-03-14

    Good understanding of the reaction mechanism in the electrochemical reduction of water to hydrogen is crucial to renewable energy technologies. Although previous studies have revealed that the surface properties of materials affect the catalytic reactivity, the effects of a catalytic surface on the hydrogen evolution reaction (HER) on the molecular level are still not well understood. Contrary to general belief, water molecules do not adsorb onto the surfaces of 3C-SiC nanocrystals (NCs), but rather spontaneously dissociate via a surface autocatalytic process forming a complex consisting of -H and -OH fragments. In this study, we show that ultrathin 3C-SiC NCs possess superior electrocatalytic activity in the HER. This arises from the large reduction in the activation barrier on the NC surface enabling efficient dissociation of H(2)O molecules. Furthermore, the ultrathin 3C-SiC NCs show enhanced HER activity in photoelectrochemical cells and are very promising to the water splitting based on the synergistic electrocatalytic and photoelectrochemical actions. This study provides a molecular-level understanding of the HER mechanism and reveals that NCs with surface autocatalytic effects can be used to split water with high efficiency thereby enabling renewable and economical production of hydrogen.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Electrochemical fabrication of surface chemical gradients in thiol self-assembled monolayers with tailored work-functions.

    PubMed

    Fioravanti, Giulia; Lugli, Francesca; Gentili, Denis; Mucciante, Vittoria; Leonardi, Francesca; Pasquali, Luca; Liscio, Andrea; Murgia, Mauro; Zerbetto, Francesco; Cavallini, Massimiliano

    2014-10-01

    The studies on surface chemical gradients are constantly gaining interest both for fundamental studies and for technological implications in materials science, nanofluidics, dewetting, and biological systems. Here we report on a new approach that is very simple and very efficient, to fabricate surface chemical gradients of alkanethiols, which combines electrochemical desorption/partial readsorption, with the withdrawal of the surface from the solution. The gradient is then stabilized by adding a complementary thiol terminated with a hydroxyl group with a chain length comparable to desorbed thiols. This procedure allows us to fabricate a chemical gradient of the wetting properties and the substrate work-function along a few centimeters with a gradient slope higher than 5°/cm. Samples were characterized by cyclic voltammetry during desorption, static contact angle, XPS analysis, and Kelvin probe. Computer simulations based on the Dissipative Particle Dynamics methods were carried out considering a water droplet on a mixed SAM surface. The results help to rationalize the composition of the chemical gradient at different position on the Au surface.

  18. Electrochemical surface science twenty years later: Expeditions into the electrocatalysis of reactions at the core of artificial photosynthesis

    NASA Astrophysics Data System (ADS)

    Soriaga, Manuel P.; Baricuatro, Jack H.; Cummins, Kyle D.; Kim, Youn-Geun; Saadi, Fadl H.; Sun, Guofeng; McCrory, Charles C. L.; McKone, James R.; Velazquez, Jesus M.; Ferrer, Ivonne M.; Carim, Azhar I.; Javier, Alnald; Chmielowiec, Brian; Lacy, David C.; Gregoire, John M.; Sanabria-Chinchilla, Jean; Amashukeli, Xenia; Royea, William J.; Brunschwig, Bruce S.; Hemminger, John C.; Lewis, Nathan S.; Stickney, John L.

    2015-01-01

    Surface science research fixated on phenomena and processes that transpire at the electrode-electrolyte interface has been pursued in the past. A considerable proportion of the earlier work was on materials and reactions pertinent to the operation of small-molecule fuel cells. The experimental approach integrated a handful of surface-sensitive physical-analytical methods with traditional electrochemical techniques, all harbored in a single environment-controlled electrochemistry-surface science apparatus (EC-SSA); the catalyst samples were typically precious noble metals constituted of well-defined single-crystal surfaces. More recently, attention has been diverted from fuel-to-energy generation to its converse, (solar) energy-to-fuel transformation; e.g., instead of water synthesis (from hydrogen and oxygen) in fuel cells, water decomposition (to hydrogen and oxygen) in artificial photosynthesis. The rigorous surface-science protocols remain unchanged but the experimental capabilities have been expanded by the addition of several characterization techniques, either as EC-SSA components or as stand-alone instruments. The present manuscript describes results selected from on-going studies of earth-abundant electrocatalysts for the reactions that underpin artificial photosynthesis: nickel-molybdenum alloys for the hydrogen evolution reaction, calcium birnessite as a heterogeneous analogue for the oxygen-evolving complex in natural photosynthesis, and single-crystalline copper in relation to the carbon dioxide reduction reaction.

  19. 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.

  20. Electrochemical oxidation of the chalcopyrite surface: an XPS and AFM study in solution at pH 4

    NASA Astrophysics Data System (ADS)

    Farquhar, Morag L.; Wincott, Paul L.; Wogelius, Roy A.; Vaughan, David J.

    2003-09-01

    The electrochemical oxidation of chalcopyrite (CuFeS 2) has been studied at pH 4 using voltammetry, coulometry, X-ray photoelectron spectroscopy (XPS) and both ex situ and in situ atomic force microscopy (AFM). Between 500 and 650 mV an anodic oxidation peak is observed, prior to the onset of the main decomposition reactions. Chalcopyrite electrodes in contact with electrolyte show some release of Cu into solution even without an applied potential. At 500 and 650 mV, the loss of Cu from the surface increases by a factor of 2 and 6, respectively. Oxidation at 500 mV results in the formation of a mixed oxide or hydroxide of iron, coincident with islands (<0.15 μm wide) of reaction products observed on the surface using AFM. The surface coverage of these islands increases with amount of charge passed. Oxidation at 650 mV shows similar processes have occurred, but with a greater island surface coverage and a more deeply altered surface. XPS depth profiling suggests iron oxide or hydroxide is now a major phase in the top ˜40 Å, with significant sulphate also formed. Observation of islands (alteration products) using in situ AFM under potential control shows that these features are not an artefact of the preparation methods.

  1. Pulsed electrochemical micromachining for generating micro-dimple arrays on a cylindrical surface with a flexible mask

    NASA Astrophysics Data System (ADS)

    Chen, Xiaolei; Qu, Ningsong; Li, Hansong; Xu, Zhengyang

    2015-07-01

    Micro-dimple arrays play an important role in improving the performance and reliability of mechanical systems, and micro-dimples on the surfaces of piston rings and sliding bearings may reduce friction. Although many methods can be employed to create micro-dimples on cylindrical surfaces, it is still a challenge to generate micro-dimple arrays on cylindrical surfaces with high efficiency and low cost. In this paper, a patterned polydimethylsiloxane (PDMS) mask with good flexibility is introduced as a mask in through-mask electrochemical micromachining (TMEMM) for generating micro-dimple arrays on a cylindrical surface, in which thousands of micro-dimples can be fabricated in tens of seconds. In addition, the reusability of the PDMS mask is experimentally verified. To enhance removal of the product, the use of a pulsed current is introduced into TMEMM of micro-dimples. The experimental results show that the pulse duty cycle plays a significant role in enhancing the removal of product and improving the uniformity of the micro-dimple arrays. And the effect was weakened with increasing pulse duty cycle. Compared with duty cycles of 40, 60, and 80%, the highest current efficiency with a duty cycle of 20% is obtained at a frequency of 10 kHz. Finally, micro-dimple arrays with a diameter of approximately 110.6 μm and a depth of 11 μm are successfully generated on the cylindrical surface.

  2. 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.

  3. Synthesis and characterization of high surface area molybdenum nitride electrodes for high energy density electrochemical storage devices

    NASA Astrophysics Data System (ADS)

    Roberson, Scott Lee

    1998-12-01

    Polycrystalline high surface area (>20 msp2/g) Mosb{x}N (x = 1 and 2) films have been synthesized by the conversion of MoOsb3 films in controlled temperature reactions with NHsb3 and by chemical vapor deposition (CVD) of either MoClsb5 or Mo(CO)sb6 and NHsb3. The formation of larger surface areas was achieved in films that were converted form MoOsb3; however, control of the composition of the Mosb{x}N films was achieved only by CVD. The increase in surface areas in the converted samples was credited to both the increase in specific density of the film during the conversion to Mosb{x}N and the topotactic nature of the conversion. Compositional control of the CVD Mosb{x}N films was accomplished by varying the deposition rate, the precursor employed, the deposition temperature and the NHsb3 flow rate. The electrochemical stability of the converted and CVD Mosb{x}N films occurred between ≈0.5 and ≈0.70 V vs. a standard hydrogen electrode (SHE). Control of the composition of the CVD Mosb{x}N films allowed the determination of the electrochemical stabilities of each phase (gamma-Mosb2N and delta-MoN). The CVD Mosb{x}N films were subsequently used as cathodes for the fabrication of hybrid capacitor devices. These devices were operational between 0-50 V and had a total capacitance of 5.0 mF at 1 V. Both the operating voltage and the capacitance of these devices are higher than devices currently used in government and medical applications.

  4. 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…

  5. 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...

  6. 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.

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

    DOE PAGESBeta

    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, 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

  8. 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

  9. 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.

  10. 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.

  11. 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

    2015-12-01

    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. PMID:26524187

  12. Surface characteristics and electrochemical corrosion behavior of a pre-anodized microarc oxidation coating on titanium alloy.

    PubMed

    Cui, W F; Jin, L; Zhou, L

    2013-10-01

    A porous bioactive titania coating on biomedical β titanium alloy was prepared by pre-anodization followed by micro arc oxidation technology. The effects of pre-anodization on the phase constituent, morphology and electrochemical corrosion behavior of the microarc oxidation coating were investigated. The results show that pre-anodization has less influence on the phase constituent and the surface morphology of the microarc oxidation coating, but improves the inner layer density of the microarc oxidation coating. The decrease of plasma discharge strength due to the presence of the pre-anodized oxide film contributes to the formation of the compact inner layer. The pre-anodized microarc oxidation coating effectively inhibits the penetration of the electrolyte in 0.9% NaCl solution and thus increases the corrosion resistance of the coated titanium alloy in physiological solution.

  13. 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.

  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. 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

  16. 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

    2015-01-01

    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

  17. 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

  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 PAGESBeta

    Patete, Jonathan M.; Wong, Stanislaus S.; Scofield, Megan E.; Volkov, Vyacheslav; Koenigsmann, Christopher; Zhang, Yiman; Marschilok, Amy C.; Wang, Xiaoya; Bai, Jianming; Han, Jinkyu; et al

    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. 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.

  1. Surface Tension Measurements on Oleochemicals Derived from Soybean Oil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We report the surface tension measurements, at a variety of temperatures, for a variety of alkyl esters; in olefinic, epoxy, and branched ester forms. Because these compounds are potential fuel or lubricant additives, this physical data is valuable, and currently unreported in the literature. For ...

  2. Spectroscopic and electrochemical characterization of the surface layers of chalcopyrite (CuFeS 2) reacted in acidic solutions

    NASA Astrophysics Data System (ADS)

    Mikhlin, Yuri L.; Tomashevich, Yevgeny V.; Asanov, Igor P.; Okotrub, Alexander V.; Varnek, Vladimir A.; Vyalikh, Denis V.

    2004-03-01

    XPS, Fe Lα,β and Cu Lα,β X-ray emission and Fe L-, Cu L-, S L-edge and O K-edge absorption spectroscopies, Mössbauer spectroscopy and cyclic voltammetry were applied to study reacted surface layers of natural chalcopyrite, CuFeS 2. The surfaces became metal-depleted after the anodic oxidation in 1 M HCl and the leaching in 1 M H 2SO 4+0.2 M Fe 2(SO 4) 3 or 1 M HCl+0.4 M FeCl 3 solutions, with the sulfur excess and iron/copper ratio been higher in the last instance, and were enriched in copper after the electrochemical reduction. The electronic structures of the metal-deficient layers up to several tenths of micrometer thick were similar to that of chalcopyrite, except that the density of the highest occupied states depended on sulfur anions formed (predominant S 3-anions after the ferric sulfate treatment, S 4-anions after the ferric chloride leaching or the potential sweep to 0.9 V, etc.). The layers created by the preliminary oxidation had only a small effect on the chalcopyrite voltammetry. We suggest a new reaction mechanism considering a role of the surface changes, including disordering and Anderson localization of the electronic states.

  3. Using electrochemical surface plasmon resonance for in-situ kinetic investigations of solid electrolyte interphase formation in lithium ion battery

    NASA Astrophysics Data System (ADS)

    Pradanawati, Sylvia Ayu; Wang, Fu-Ming; Su, Chia-Hung

    2016-10-01

    The solid electrolyte interphase (SEI) significantly affects the energy density and safety performance of lithium ion batteries. Previous studies have shown that conventional analyses cannot characterize the real-time molecule interactions of SEI formation on the surface of an electrode. In this study, a novel in situ electrochemical-surface plasmon resonance (EC-SPR) was developed for evaluating the kinetic changes of ionic dissociation, SEI formation, and Li-Au alloying reaction. The novel EC-SPR not only indicates the rates of each reaction stage but also reveals the characteristics of the passivated layers. This research demonstrates that the dissociation rates of ionic clusters are affected by several reactions on the surface of an electrode. The rate and mass of the SEI formation from the reduction of ethylene carbonate (EC) are calculated at 0.004 ngs-1 and 5.858 ng, respectively. The EC-SPR is a powerful tool for further in situ kinetic investigations of different electrolyte and electrode systems.

  4. 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

  5. Electrochemical patterning of the surface of insulators with electrically conductive polymers

    SciTech Connect

    Zheng, X.Y.; Ding, Y.; Bottomley, L.A.

    1995-12-01

    The great potential of {pi}-conjugated polymers, especially polyacetylene, polyarylenes, and poly(arylenevinylene)s, as components in optical displays, sensors, rechargeable batteries, electromagnetic interference shielding, and microelectronics is well recognized. This paper presents a protocol for patterning the surface of insulators with electrically conductive polymers. The pattern is formed on a gold electrode surface via electro-oxidation of heteroarene monomers. An adhesion layer is used to bond the surface of the conducting polymer pattern to the surface of an insulator. The pattern is then developed by etching away the gold. The approach is illustrated with polypyrrole and is applicable to a wide range of substituted polyheteroarenes and insulating substrates.

  6. 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. PMID:26085116

  7. New metal based drugs: spectral, electrochemical, DNA-binding, surface morphology and anticancer activity properties.

    PubMed

    Çeşme, Mustafa; Gölcü, Aysegul; Demirtaş, Ibrahim

    2015-01-25

    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.

  8. 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.

  9. Preparation, surface characteristics and electrochemical properties of electrophoretically deposited C60 films

    SciTech Connect

    Kutner, Wlodzimierz; Pieta, Piotr; Nowakowski, Robert; Sobczak, Janusz W.; Kaszkur, Zbigniew

    2005-09-27

    Thin fullerene films of controlled roughness were electrophoretically deposited from C60 suspensions formed in mixed toluene-ethanol solutions. Mass of the deposited films, determined by piezoelectric microgravimetry (PM) with the use of an electrochemical quartz crystal microbalance, exponentially increased with time. Size of the AFM imaged C60 grains in the films depended both on time of C60 aggregation in bulk solution prior to deposition and strength of the electric field applied. In the accessible potential range, cyclic voltammetry (CV) curves for the films in 0.1 M (TBA)PF6, in acetonitrile, featured four main cathodic peaks formed during the negative potential excursion. These peaks corresponded to four one-electron reductions. Simultaneously recorded PM and CV curves showed an overall mass decrease, corresponding to stepwise C60 electroreduction and the complete dissolution of the C{sub 60}{sup 3-} film. The CV, XPS and XRD analyses indicated the film swelling and reversible ingress of both TBA+ counter- and PF{sub 6}{sup -} co-ion into the C{sub 60}{sup -} film.

  10. 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.

  11. 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.

  12. 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.

  13. Computerized craniofacial reconstruction using CT-derived implicit surface representations.

    PubMed

    Vandermeulen, Dirk; Claes, Peter; Loeckx, Dirk; De Greef, Sven; Willems, Guy; Suetens, Paul

    2006-05-15

    In forensic craniofacial reconstruction, facial features of an unknown individual are estimated from an unidentified skull, based on a mixture of experimentally obtained guidelines on the relationship between soft tissues and the underlying skeleton. In this paper, we investigate the possibility of using full 3D cross-sectional CT images for establishing a reference database of densely sampled distances between the external surfaces of the skull and head for automated craniofacial reconstruction. For each CT image in the reference database, the hard tissue (skull) and soft tissue (head) volumes are automatically segmented and transformed into signed distance transform (sDT) images, representing for each voxel in this image the Euclidean distance to the closest point on the skull and head surface, respectively, distances being positive (negative) for voxels inside (outside) the skull/head. Multiple craniofacial reconstructions are obtained by first warping each reference skull sDT maps to the target skull sDT using a B-spline based free form deformation algorithm and subsequently applying these warps to the reference head sDT maps. A single reconstruction of the target head surface is defined as the zero level set of the arithmetic average of all warped reference head sDT maps, but other reconstructions are possible, biasing the result to subject specific attributes (age, BMI, gender). Both qualitative and quantitative tests (measuring the similarity between the 3D reconstructed and corresponding original head surface) on a small (N = 20) database are presented to proof the validity of the concept.

  14. The satellite altimeter data derived mean sea surface GSFC98

    NASA Astrophysics Data System (ADS)

    Wang, Yan M.

    2000-03-01

    The GSFC98 mean sea surface (MSS) was computed on a 2' oceanwide grid for latitudes below 80°. The data used included 3-years of TOPEX data (Cycles 9 to 119), 1.5-years of ERS-1 35-day repeat cycle (Cycles 1 to 18), 2-years of Geosat ERM data (Cycles 1 to 42), 2 ERS-1 168-day repeat cycles, and 18 months of the Geosat Geodetic Mission data. All non-TOPEX satellite altimeter data were adjusted to the mean of TOPEX data in 2° × 30° blocks. After the adjustment, the mean sea surface height was gridded into 2' nodes using least squares collocation and an iteration procedure to reduce the ocean variability. To validate the mean sea surfaces, three comparisons were made. The GSFC98 MSS, along with OSU95 [Yi, 1995] and CSR95 [Kim et al., 1995], were compared with 6-years of TOPEX and 3-years of ERS-2 mean tracks which were not used in the MSS computations. Finally, the marine gravity anomalies were computed from the three MSS implied geoid undulations using the inverse Stokes integral. The marine gravity anomalies were compared with ship gravity data in selected areas. The ship gravity comparison is an independent assessment of the quality of the MSSs, especially at intermediate and short wavelengths. Finally, the inter-comparisons between the mean sea surfaces were made. The root mean square values of the differences were 6.8, 6.8, and 7.2 cm between GSFC98/OSU95, GSFC98/CSR95, and OSU95/CSR95. The differences agree well with the error estimation of GSFC98 MSS.

  15. Correcting Satellite Image Derived Surface Model for Atmospheric Effects

    NASA Technical Reports Server (NTRS)

    Emery, William; Baldwin, Daniel

    1998-01-01

    This project was a continuation of the project entitled "Resolution Earth Surface Features from Repeat Moderate Resolution Satellite Imagery". In the previous study, a Bayesian Maximum Posterior Estimate (BMPE) algorithm was used to obtain a composite series of repeat imagery from the Advanced Very High Resolution Radiometer (AVHRR). The spatial resolution of the resulting composite was significantly greater than the 1 km resolution of the individual AVHRR images. The BMPE algorithm utilized a simple, no-atmosphere geometrical model for the short-wave radiation budget at the Earth's surface. A necessary assumption of the algorithm is that all non geometrical parameters remain static over the compositing period. This assumption is of course violated by temporal variations in both the surface albedo and the atmospheric medium. The effect of the albedo variations is expected to be minimal since the variations are on a fairly long time scale compared to the compositing period, however, the atmospheric variability occurs on a relatively short time scale and can be expected to cause significant errors in the surface reconstruction. The current project proposed to incorporate an atmospheric correction into the BMPE algorithm for the purpose of investigating the effects of a variable atmosphere on the surface reconstructions. Once the atmospheric effects were determined, the investigation could be extended to include corrections various cloud effects, including short wave radiation through thin cirrus clouds. The original proposal was written for a three year project, funded one year at a time. The first year of the project focused on developing an understanding of atmospheric corrections and choosing an appropriate correction model. Several models were considered and the list was narrowed to the two best suited. These were the 5S and 6S shortwave radiation models developed at NASA/GODDARD and tested extensively with data from the AVHRR instrument. Although the 6S model

  16. 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. PMID:27295099

  17. 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.

  18. 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.

  19. Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

    NASA Astrophysics Data System (ADS)

    Meng, Jianbing; Dong, Xiaojuan; Wei, Xiuting; Yin, Zhanmin

    2014-03-01

    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.

  20. 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.

  1. 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.

  2. Controlling the Adsorption of Ruthenium Complexes on Carbon Surfaces through Noncovalent Bonding with Pyrene Anchors: An Electrochemical Study.

    PubMed

    Kohmoto, Mayuko; Ozawa, Hiroaki; Yang, Li; Hagio, Toshihiro; Matsunaga, Mariko; Haga, Masa-Aki

    2016-05-01

    Surface modifications of carbon nanomaterials, such as graphene or carbon nanotubes, through noncovalent π-π interactions between π-conjugated carbon surfaces and pyrene anchors have received much attention on account of the applications of these materials in organic electronic and sensor devices. Despite the rapidly expanding use of pyrene anchors, little is known about the number of pyrene groups required in order to achieve a stable attachment of molecules on nanocarbon surfaces. So far, systematic studies on such surface modifications through adsorption isotherms and desorption behavior of molecules still remain scarce. In this study, we have investigated the effect of the number of pyrene anchors in redox-active Ru complexes on their adsorption on carbon nanomaterials through noncovalent π-π interactions. The Ru(II/III) couple was used as a redox marker in order to determine the surface coverage on nanocarbon surfaces such as highly oriented pyrolytic graphite (HOPG), single-walled carbon nanotubes (SWCNTs), and multiwalled carbon nanotubes (MWCNTs). The amount of surface coverage as well as the kinetic stability of the Ru complexes was thereby observed to be directly proportional to the number of pyrene groups present in the ligands. The desorption rate from HOPG electrode increased in the order Ru-1 with eight pyrene groups (k = 2.0 × 10(-5) s(-1)) < Ru-2 with four pyrenes (4.1 × 10(-5) s(-1)) < Ru-3 with two pyrenes (6.8 × 10(-5) s(-1)) ≪ Ru-4 with one pyrene (4.1 × 10(-3) s(-1)). Furthermore, the electrochemical polymerization of the Ru complex with four pyrene groups proceeded more efficiently compared to complexes with one or two pyrene groups. As a consequence, compounds having more than two and/or optimally four pyrene groups revealed a stable adsorption on the nanocarbon surfaces. The heterogeneous electron transfer rate between the Ru complex, Ru-2, and the carbon nanomaterials increased in the order SWCNTs (kET = 1.3 s(-1)) < MWCNTs (

  3. 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

    2013-05-01

    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

  4. 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

    2013-05-01

    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

  5. 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.

  6. 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

  7. Electrochemical Sensors Based on Screen-Printed Electrodes: The Use of Phthalocyanine Derivatives for Application in VFA Detection.

    PubMed

    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

  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

    2015-01-01

    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. PMID:26035095

  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

    Ndiaye, Amadou L; Delile, Sébastien; Brunet, Jérôme; Varenne, Christelle; Pauly, Alain

    2016-09-01

    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.

  11. 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.

  12. Factors affecting the electrochemical regeneration of NADH by (2,2'-bipyridyl) (pentamethylcyclopentadienyl)-rhodium complexes: impact on their immobilization onto electrode surfaces.

    PubMed

    Walcarius, Alain; Nasraoui, Rihab; Wang, Zhijie; Qu, Fengli; Urbanova, Veronika; Etienne, Mathieu; Göllü, Mehmet; Demir, Ayhan S; Gajdzik, Janine; Hempelmann, Rolf

    2011-08-01

    Complexes of the (2,2'-bipyridyl) (pentamethylcyclopentadienyl)-rhodium family ([Cp*Rh(bpy)Cl](+), which is actually hydrolyzed in the form of [Cp*Rh(bpy)H(2)O](2+) in aqueous medium) are suitable solution-phase mediators likely to regenerate nicotinamide cofactors associated to dehydrogenases involved in many biocatalytic applications. Their practical application as bioelectrocatalysts, e.g., in fine chemicals synthesis or biosensors, remains however restricted to their durable immobilization in an active form onto solid electrode surfaces. This paper reports some new observations on the electrocatalytic properties of this mediator towards NAD(+) reduction, notably the critical effect of pH and cofactor-to-mediator concentration ratio, and investigates the behavior of a series of ([Cp*Rh(bpy)Cl](+)) derivatives bearing various substituents on the bipyridine ligand in view of their subsequent integration in electrochemical bioreactors. It will be shown that such compounds containing S- or N- moieties (i.e., often used as precursors to functionalize electrode surfaces) lead to inactivation of the electrocatalyst because their interaction with the Rh center prevents the formation of the active rhodium hydride complex. It was thus necessary to find another strategy of immobilization, and we found that adsorption of [Cp*Rh(bpy)Cl](+) by π-stacking on single-walled carbon nanotubes is an effective mean to reach this goal, leading to efficient and stable catalytic responses for NAD(+) reduction. Preliminary electroenzymatic experiments in the presence of d-sorbitol dehydrogenase further point out the interest of this approach for bioelectrocatalysis purposes and provide the proof-of-concept for this immobilization strategy. PMID:21700510

  13. Factors affecting the electrochemical regeneration of NADH by (2,2'-bipyridyl) (pentamethylcyclopentadienyl)-rhodium complexes: impact on their immobilization onto electrode surfaces.

    PubMed

    Walcarius, Alain; Nasraoui, Rihab; Wang, Zhijie; Qu, Fengli; Urbanova, Veronika; Etienne, Mathieu; Göllü, Mehmet; Demir, Ayhan S; Gajdzik, Janine; Hempelmann, Rolf

    2011-08-01

    Complexes of the (2,2'-bipyridyl) (pentamethylcyclopentadienyl)-rhodium family ([Cp*Rh(bpy)Cl](+), which is actually hydrolyzed in the form of [Cp*Rh(bpy)H(2)O](2+) in aqueous medium) are suitable solution-phase mediators likely to regenerate nicotinamide cofactors associated to dehydrogenases involved in many biocatalytic applications. Their practical application as bioelectrocatalysts, e.g., in fine chemicals synthesis or biosensors, remains however restricted to their durable immobilization in an active form onto solid electrode surfaces. This paper reports some new observations on the electrocatalytic properties of this mediator towards NAD(+) reduction, notably the critical effect of pH and cofactor-to-mediator concentration ratio, and investigates the behavior of a series of ([Cp*Rh(bpy)Cl](+)) derivatives bearing various substituents on the bipyridine ligand in view of their subsequent integration in electrochemical bioreactors. It will be shown that such compounds containing S- or N- moieties (i.e., often used as precursors to functionalize electrode surfaces) lead to inactivation of the electrocatalyst because their interaction with the Rh center prevents the formation of the active rhodium hydride complex. It was thus necessary to find another strategy of immobilization, and we found that adsorption of [Cp*Rh(bpy)Cl](+) by π-stacking on single-walled carbon nanotubes is an effective mean to reach this goal, leading to efficient and stable catalytic responses for NAD(+) reduction. Preliminary electroenzymatic experiments in the presence of d-sorbitol dehydrogenase further point out the interest of this approach for bioelectrocatalysis purposes and provide the proof-of-concept for this immobilization strategy.

  14. Enhanced electrochemical performance of nanoparticle coated polyethylene separator surface for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Sivaprakash, Prabhavathy; Sen, P. K.; Sivaprakash, S.

    2014-12-01

    The separator (membrane) in a lithium ion rechargeable battery plays an indispensable role by preventing material and electrical contact of positive and negative electrodes, allowing swift ionic flow within the cell. Herein, we report an interesting approach to improve performance of readily available polyolefin separator by coating it with synthesized silica nanoparticles/polyvinylidene fluoride optimal blend. This coated composite separator was investigated for surface morphology, wettability, electrolyte uptake, thermal stability and performance studies. Coin cells fabricated using surface coated separator show good C-rate capability and stable cycle performance with capacity retention of 99% even after 50 cycles.

  15. 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

  16. 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.

  17. Aligned/micropatterned carbon nanotube arrays: surface functionalization and electrochemical sensing

    NASA Astrophysics Data System (ADS)

    Qu, Liangti; He, Pingang; Li, Lingchuan; Gao, Mei; Wallace, Gordon; Dai, Liming

    2005-03-01

    We have previously developed a simple pyrolytic method for large-scale production of aligned multi-wall carbon nanotube arrays perpendicular to the substrate. These aligned carbon nanotube arrays can be transferred onto various substrates of particular interest (e.g. polymer films for organic optoelectronic devices) in either a patterned or non-patterned fashion. The well-aligned structure provides additional advantages for not only an efficient device construction but also for surface functionalization. The surface functionalization of aligned carbon nanotubes is particularly attractive, as it allows surface characteristics of the aligned carbon nanotubes to be tuned to meet specific requirements for particular applications while their alignment structure can be largely retained. These aligned carbon nanotubes with tunable surface characteristics are of great significance to various practical applications ranging from sensors to electronics. Single-strand DNA chains could be covalently immobilized onto plasma-activated aligned carbon nanotubes for sensing complementary DNA and/or target DNA chains of specific sequences with a high sensitivity and selectivity. Furthermore, glucose oxidase (GOX) could also be immobilized onto the aligned carbon nanoutbe arrays by electropolymerization of pyrrole in the presence of GOX. The resultant GOX-containing polypyrrole-carbon nanotube coaxial nanowires were shown to be promising new sensing active materials for making advanced glucose sensors with a high sensitivity.

  18. 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

  19. Impact of electrolyte composition on the reactivity of a redox active polymer studied through surface interrogation and ion-sensitive scanning electrochemical microscopy.

    PubMed

    Burgess, Mark; Hernández-Burgos, Kenneth; Cheng, Kevin J; Moore, Jeffrey S; Rodríguez-López, Joaquín

    2016-06-21

    Elucidating the impact of interactions between the electrolyte and electroactive species in redox active polymers is key to designing better-performing electrodes for electrochemical energy storage and conversion. Here, we present on the improvement of the electrochemical activity of poly(para-nitrostyrene) (PNS) in solution and as a film by exploiting the ionic interactions between reduced PNS and K(+), which showed increased reactivity when compared to tetrabutylammonium (TBA(+))- and Li(+)-containing electrolytes. While cyclic voltammetry enabled the study of the effects of cations on the electrochemical reversibility and the reduction potential of PNS, scanning electrochemical microscopy (SECM) provided new tools to probe the ionic and redox reactivity of this system. Using an ion-sensitive Hg SECM tip allowed to probe the ingress of ions into PNS redox active films, while surface interrogation SECM (SI-SECM) measured the specific kinetics of PNS and a solution phase mediator in the presence of the tested electrolytes. SI-SECM measurements illustrated that the interrogation kinetics of PNS in the presence of K(+) compared to TBA(+) and Li(+) are greatly enhanced under the same surface concentration of adsorbed radical anion, exhibiting up to a 40-fold change in redox kinetics. We foresee using this new application of SECM methods for elucidating optimal interactions that enhance polymer reactivity for applications in redox flow batteries.

  20. 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.

  1. Quantitative relationships between structure and cytotoxic activity of flavonoid derivatives. An application of Hirshfeld surface derived descriptors.

    PubMed

    Kupcewicz, Bogumiła; Małecka, Magdalena; Zapadka, Mariusz; Krajewska, Urszula; Rozalski, Marek; Budzisz, Elzbieta

    2016-07-15

    Quantitative relationships between the structure and cytotoxic activity of series flavonoid derivatives were examined. The first regression-based model, developed for 18 flavanone-2-pyrazoline hybrids, involved two interpretable descriptors: a Mor04v and partial atomic charge. The second model, developed for structurally diverse set of compounds, was based on descriptors derived from Hirshfeld surface analysis. This model suggests that cytotoxic activity of compounds can be successfully predicted based on a fraction of H⋯H contacts and a fraction of interactions involving a halogen atom. For non-halogen derivatives, the data reveal that cytotoxic activity is inversely proportional to the percentage of O⋯H and N⋯H close contacts to Hirshfeld surface, while directly proportional to the percentage of H⋯H interactions. Chlorine (1k) and bromine (1l) derivatives of compounds, containing flavanone fused with N-methyl-2-pyrazoline, exhibited high cytotoxic potential against HL-60 cancer cell line (IC50<10μM). The cytotoxicity of 1k and 1l towards normal cells (HUVEC) was 10 and 25-fold lower, respectively. PMID:27234147

  2. Quantitative relationships between structure and cytotoxic activity of flavonoid derivatives. An application of Hirshfeld surface derived descriptors.

    PubMed

    Kupcewicz, Bogumiła; Małecka, Magdalena; Zapadka, Mariusz; Krajewska, Urszula; Rozalski, Marek; Budzisz, Elzbieta

    2016-07-15

    Quantitative relationships between the structure and cytotoxic activity of series flavonoid derivatives were examined. The first regression-based model, developed for 18 flavanone-2-pyrazoline hybrids, involved two interpretable descriptors: a Mor04v and partial atomic charge. The second model, developed for structurally diverse set of compounds, was based on descriptors derived from Hirshfeld surface analysis. This model suggests that cytotoxic activity of compounds can be successfully predicted based on a fraction of H⋯H contacts and a fraction of interactions involving a halogen atom. For non-halogen derivatives, the data reveal that cytotoxic activity is inversely proportional to the percentage of O⋯H and N⋯H close contacts to Hirshfeld surface, while directly proportional to the percentage of H⋯H interactions. Chlorine (1k) and bromine (1l) derivatives of compounds, containing flavanone fused with N-methyl-2-pyrazoline, exhibited high cytotoxic potential against HL-60 cancer cell line (IC50<10μM). The cytotoxicity of 1k and 1l towards normal cells (HUVEC) was 10 and 25-fold lower, respectively.

  3. 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.

  4. Protein-inorganic hybrid nanoflowers as ultrasensitive electrochemical cytosensing interfaces for evaluation of cell surface sialic acid.

    PubMed

    Cao, Hongmei; Yang, Da-Peng; Ye, Daixin; Zhang, Xianxia; Fang, Xueen; Zhang, Song; Liu, Baohong; Kong, Jilie

    2015-06-15

    The identification of biocompatible nanomaterials with high conductivities as sensing interfaces is important in developing novel electrochemical cytosensors. We prepared a novel protein-inorganic nanomaterial-bovine serum albumin (BSA) incorporated Ag nanoflowers with three-dimensional porous architectures, using a simple biomimetic method. The BSA-incorporated Ag nanoflowers were modified on a glassy carbon electrode (GCE) surface and conjugated with a targeting lectin molecule, i.e., Sambucus nigra agglutinin (SNA), for sensing DLD-1 human colon cancer cells. The BSA-incorporated Ag nanoflowers were a suitable platform, and showed improved cell-immobilization capacity, and good biocompatibility, with retention of activity of the immobilized cells. These properties are attributed to the large surface area of the porous structure and the natural BSA layer acting as a biocompatible support. The attachment of DLD-1 cells to the GCE increased the electron-transfer resistance, with a good correlation with the logarithm of the concentration from 1.35×10(2) to 1.35×10(7) cells mL(-1), with a low detection limit of 40 cells mL(-1). Based on the affinity between SNA and sialic acid (SA), the UV-vis absorption spectrum of the one-step reaction between SA and acidic ninhydrin indicated that the average number of SA molecules on a single living DLD-1 cell surface was approximately 2.16×10(12). This proposed cytosensing strategy had good reproducibility, acceptable precision, and high specificity for SA-over-expressed cells, indicating that it has potential applications for the early monitoring of tumor cells and convenient evaluation of SA on living cells. PMID:25599845

  5. 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.

  6. Effect of surface finishing on early-stage corrosion of a carbon steel studied by electrochemical and atomic force microscope characterizations

    NASA Astrophysics Data System (ADS)

    Li, Yuan; Cheng, Y. Frank

    2016-03-01

    In this work, the early-stage corrosion of a carbon steel with various surface roughness, which was created by different levels of surface finishing treatment, was characterized by an atomic force microscope and electrochemical measurements. It is found that the resulting surface roughness is at nano-meter scale. As the surface roughness increases, the corrosion activity of the steel is increased. The early-stage corrosion of the steel is featured with two stages of dissolution. While the first stage involves a rapid dissolution and increasing surface roughness of the steel, stage two is in an equilibrium state to have an approximately constant corrosion rate and surface roughness. Generally, the corrosion rate of the steel decreases when the surface finish of the specimen becomes finer. Local preferential corrosion occurs at surface irregularities, resulting in the deepening and widening of the features such as scratches with time.

  7. Pulse electrochemical machining on Invar alloy: Optical microscopic/SEM and non-contact 3D measurement study of surface analyses

    NASA Astrophysics Data System (ADS)

    Kim, S. H.; Choi, S. G.; Choi, W. K.; Yang, B. Y.; Lee, E. S.

    2014-09-01

    In this study, Invar alloy (Fe 63.5%, Ni 36.5%) was electrochemically polished by PECM (Pulse Electro Chemical Machining) in a mixture of NaCl, glycerin, and distilled water. A series of PECM experiments were carried out with different voltages and different electrode shapes, and then the surfaces of polished Invar alloy were investigated. The polished Invar alloy surfaces were investigated by optical microscope, scanning electron microscope (SEM), and non-contact 3D measurement (white light microscopes) and it was found that different applied voltages produced different surface characteristics on the Invar alloy surface because of the locally concentrated applied voltage on the Invar alloy surface. Moreover, we found that the shapes of electrode also have an effect on the surface characteristics on Invar alloy surface by influencing the applied voltage. These experimental findings provide fundamental knowledge for PECM of Invar alloy by surface analysis.

  8. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    DOE PAGESBeta

    Cui, Chaonan; Han, Jinyu; Zhu, Xinli; Liu, Xiao; Wang, Hua; Mei, Donghai; Ge, Qingfeng

    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

  9. Novel Co3O4 porous polyhedrons derived from metal-organic framework toward high performance for electrochemical energy devices

    NASA Astrophysics Data System (ADS)

    Chen, Youcun; Hu, Lin

    2016-07-01

    Co3O4 polyhedrons with porous structure have been synthesized simply by annealing Prussian blue analogue (PBA) Co3[Co(CN)6]2 polyhedrons at 400 °C in air. The product was characterized by a series of techniques, such as X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM), High-resolution TEM (HRTEM), X-ray Photoelectron Spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) gas adsorption. Interestingly, when evaluated as an anode material for lithium-ion batteries (LIBs), the Co3O4 porous polyhedrons manifested high reversible capacity (about 1200 mAh g-1 at 50 mA g-1) and excellent cycling performance. Moreover, they also exhibited a high specific capacitance of 110 Fg-1 when used as an electrode in the supercapacitor. It is suggested that the special morphology and porous nanostructure lead to the promising electrochemical properties.

  10. Electrochemical synthesis of fractal bimetallic Cu/Ag nanodendrites for efficient surface enhanced Raman spectroscopy.

    PubMed

    Li, Da; Liu, Jingquan; Wang, Hongbin; Barrow, Colin J; Yang, Wenrong

    2016-09-21

    Here, we for the first time synthesized bimetallic Cu/Ag dendrites on graphene paper (Cu/Ag@G) using a facile electrodeposition method to achieve efficient SERS enhancement. Cu/Ag@G combined the electromagnetic enhancement of Cu/Ag dendrites and the chemical enhancement of graphene. SERS was ascribed to the rough metal surface, the synergistic effect of copper and silver nanostructures and the charge transfer between graphene and the molecules. PMID:27522964

  11. Electrochemical and Numerical Studies of Surface, Grain-Boundary and Bulk Copper Diffusion Into Gold

    NASA Astrophysics Data System (ADS)

    Miller, Eric Todd

    Surface, grain-boundary, and bulk chemical diffusivities of copper into gold were measured by chronoamperometry -potentiometry applied to Cu|CuCl |Au solid state galvanic cells at 300-400^circC. The cells were constructed using a novel vapor deposition technique which is described. The automated data acquisition techniques utilizing unique hardware and custom designed software are also presented. Chronoamperometry and a two electrode limited potential cyclic voltammetry technique were comparatively used to determine cell capacitance and resistance. Both gave similar RC values at lower temperatures but diverged from each other at higher temperatures. Electron hole conductivity of CuCl could not be determined from intercept values in the chronoamperometry Cottrell analysis. The partial molar enthalpy and entropy of mixing copper into gold were determined from Emf vs temperature vs composition measurements of Cu|CuCl |Au-Cu alloy cells. The results support the regular solution model of mixing with interaction energy parameter {bf{cal Q}} = 10kJ. Diffusion coefficients were calculated from the chronoamperometry-potentiometry time/flux/concentration data in two ways: via the Cottrell equation, for an average diffusion coefficient; and via a simplex and finite difference program for the simultaneous determination of surface, grain-boundary, and bulk diffusion coefficients. This program was run on a MASPAR MP-2 massively parallel computer. The surface and grain-boundary diffusivities were numerically determinable in single and polycrystalline cathodes at short diffusion times. Bulk diffusivity was determinable at short and long diffusion times and agreed with previous data. Surface diffusivity was two orders of magnitude larger than the bulk with lower activation energy. Grain -boundary diffusivity was one order of magnitude larger than the bulk with similar activation energy. The Cottrell equation was only valid at very long diffusion times due to the transient interface

  12. 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.

  13. Rapid extraction and quantitative detection of the herbicide diuron in surface water by a hapten-functionalized carbon nanotubes based electrochemical analyzer.

    PubMed

    Sharma, Priyanka; Bhalla, Vijayender; Tuteja, Satish; Kukkar, Manil; Suri, C Raman

    2012-05-21

    A solid phase extraction micro-cartridge containing a non-polar polystyrene absorbent matrix was coupled with an electrochemical immunoassay analyzer (EIA) and used for the ultra-sensitive detection of the phenyl urea herbicide diuron in real samples. The EIA was fabricated by using carboxylated carbon nanotubes (CNTs) functionalized with a hapten molecule (an amine functionalized diuron derivative). Screen printed electrodes (SPE) were modified with these haptenized CNTs and specific in-house generated anti diuron antibodies were used for bio-interface development. The immunodetection was realized in a competitive electrochemical immunoassay format using alkaline phosphatase labeled secondary anti-IgG antibody. The addition of 1-naphthyl phosphate substrate resulted in the production of an electrochemically active product, 1-naphthol, which was monitored by using differential pulse voltammetry (DPV). The assay exhibited excellent sensitivity and specificity having a dynamic response range of 0.01 pg mL(-1) to 10 μg mL(-1) for diuron with a limit of detection of around 0.1 pg mL(-1) (n = 3) in standard water samples. The micro-cartridge coupled hapten-CNTs modified SPE provided an effective and efficient electrochemical immunoassay for the real-time monitoring of pesticides samples with a very high degree of sensitivity.

  14. Efficient Electrochemical and Photoelectrochemical H2 Production from Water by a Cobalt Dithiolene One-Dimensional Metal-Organic Surface.

    PubMed

    Downes, Courtney A; Marinescu, Smaranda C

    2015-11-01

    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)).

  15. Faradaic phase transition of dibenzyl viologen on an HOPG electrode surface studied by in situ electrochemical STM and electroreflectance spectroscopy.

    PubMed

    Higashi, Tomohiro; Shigemitsu, Yasuhiro; Sagara, Takamasa

    2011-11-15

    Phase transitions of an adsorption layer of dibenzyl viologen (dBV) as a typical diaryl viologen on a basal plane of a highly oriented pyrolytic graphite (HOPG) electrode are described using voltammetry, in situ electrochemical scanning tunneling microscopy (EC-STM), and electroreflectance (ER) spectroscopy. A monolayer redox process at less negative potential than the bulk redox process was found to be the first-order faradaic phase transition between a gaslike adsorption layer of dication (dBV(2+)) and a 2D condensed monolayer of radical cation (dBV(•+)). Comparison of the results of cyclic voltammetry and potential step chronoamperometry was made with those of heptyl viologen (HV), which also undergoes a faradaic phase transition of the first order. It suggested that the contribution of intermolecular π-π interaction between benzyl groups of dBV to the phase transition is minor and apparently equivalent to interchain interaction between the heptyl chains of HV. In situ EC-STM images of the 2D condensed monolayer demonstrated stripe patterns of the rows of dBV(•+) molecules forming 3-fold rotationally symmetric domains. The results of the ER measurements also revealed that the orientation of the longitudinal molecular axis of the bipyridinium moiety of dBV(•+) molecules lying flat on the HOPG electrode surface, most likely with a side-on configuration.

  16. Electrochemical detection of point mutation based on surface hybridization assay conjugated allele-specific polymerase chain reaction.

    PubMed

    Huang, Yong; Zhu, Jing; Li, Guiyin; Chen, Zhencheng; Jiang, Jian-Hui; Shen, Guo-Li; Yu, Ru-Qin

    2013-04-15

    In this work, we developed an electrochemical detection method based on allele-specific polymerase chain reaction (AS-PCR) and surface hybridization assay technique for the point mutation detection. A high-fidelity Vent(R)™(exo⁻) DNA polymerase, which eliminated the 3'→5' proofreading exonuclease activity by genetical engineering, was used to discriminate and extend the detection probe that perfectly matched with mutant target DNA and generate a redox-active DNA replica which folded into a molecular beacon structure by intramolecular hybridization. After hybridized with capture probe modified on gold electrode by self-assembly reaction, the redox tags can be closed to electrode, resulting in a substantial current with the maximized sensitivity for point mutation analysis. However, when there is an allele mismatch in the wild target DNA, and so no the redox-active replica DNA can be obtained. In this case, no remarkable current signal can be trigged. The proposed approach has been successfully implemented for the identification of single base mutation at the -28 position in human β-globin gene with a detection limit of 0.5 fM, demonstrating that this method provides a highly specific, sensitive and cost-efficient approach for point mutation detection.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. First principles reaction modeling of the electrochemical interface: Consideration and calculation of a tunable surface potential from atomic and electronic structure

    NASA Astrophysics Data System (ADS)

    Taylor, Christopher D.; Wasileski, Sally A.; Filhol, Jean-Sebastien; Neurock, Matthew

    2006-04-01

    A method for calculating and subsequently tuning the electrochemical potential of a half cell using periodic plane-wave density functional theory and a homogenous counter-charge is presented and evaluated by comparison to simulations which explicitly model the countercharge by a plane of ions. The method involves the establishment of two reference potentials, one related to the potential of the free electron in vacuo, and the other related to the potential of H2O species far from the electrode. The surface potential can be specifically adjusted by the explicit introduction of excess or deficit surface charges in the simulation cell and the application of periodic boundary conditions. We demonstrate the absence of field emission from the electrode over the range of realistic electrochemical potentials covered and confirm that the method can explicitly determine reaction energies and adsorption geometries as a function of electrochemical potential. This latter point is most useful as it asserts the viability of this method to model electrochemical and electrocatalytical systems of academic as well as applied interest. We present two case studies. The first examines the changes in the structure of water at the metal interface as a function of potential over Cu(111) . At cathodic potential, we observe the repulsion of H2O from the interface and the rotation of the water dipole toward the interface. The second study follows the initial pathways for the electrocatalytical activation of methanol over Pt(111) and the corresponding potential dependent reaction energetics for these paths. The results demonstrate that changes in the electrochemical potential can significantly alter the reaction energetics as well as the overall reaction selectivity. While the case studies presented herein described equilibrium geometries (i.e., the ideal forms at zero kelvin), the method is also suitable for application to ensembles of thermally activated systems.

  2. 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

  3. Enhancing electrochemical water-splitting kinetics by polarization-driven formation of near-surface iron(0): an in situ XPS study on perovskite-type electrodes.

    PubMed

    Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

    2015-02-23

    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 La0.6 Sr0.4 FeO3-δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe(0) 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.

  4. Electrochemically Driven Surface-Confined Acid/Base Reaction for an Ultrafast H(+) Supercapacitor.

    PubMed

    Gan, Shiyu; Zhong, Lijie; Gao, Lifang; Han, Dongxue; Niu, Li

    2016-02-10

    We discovered an organic weak acid, 3,4,9,10-perylene tetracarboxylic acid (PTCA), confined on the electrode surface, revealing a reversible and ultrafast protonation/deprotonation non-Faradaic process but exhibiting analogous voltammetric peaks (capacitive peaks). A further synthesized PTCA-graphene supramolecular nanocomplex discloses a wide voltage window (1.2 V) and ultrahigh specific capacitance up to 143 F g(-1) at an ultrafast charge-discharge density of 1000 A g(-1) (at least 1 order of magnitude faster than present speeds). The capacitance retention maintained at 73% after 5000 cycles. This unique capacitive voltammetric behavior suggests a new type of charge-storage modes, which may offer a way for overcoming the present difficulties of supercapacitors.

  5. 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. PMID:26149108

  6. 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

  7. 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.

  8. 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.

  9. Synthesis and Investigation of the Effect of Substitution on the Structure, Physical Properties, and Electrochemical Properties of Anthracenodifuran Derivatives.

    PubMed

    Watanabe, Motonori; Doi, Yasutaka; Hagiwara, Hidehisa; Staykov, Aleksandar Tsekov; Ida, Shintaro; Matsumoto, Taisuke; Shinmyozu, Teruo; Ishihara, Tatsumi

    2015-09-18

    A series of syn/anti mixtures of anthradifuran (ADF) and substituent compounds were systematically synthesized, and the effect of substitution at the 5,11-positions on the neutral and radical states of ADF was investigated. All compounds were measured and analyzed by absorption and fluorescence spectroscopy, cyclic voltammetry, electrochemical absorption spectroscopy, and DFT calculations. The absorption spectra of 5,11-substituent compounds in their neutral state were red-shifted. In addition, the substituted compounds exhibited increased thermal stability with respect to the parent 1a because of elongation of the π-conjugation and an increased steric hindrance effect due to the bulky ethynyl substituent groups. The cyclic voltammograms of all of the compounds exhibited irreversible reduction potentials and irreversible oxidation potentials, except in the case of (trimethylsilyl)silylethynyl-substituted ADF. When the materials were subjected to oxidation/reduction potentials, the radical cation and anion species were generated. The absorption spectra of the radical-cation species of the compounds exhibited similar characteristics and similar absorption ranges (550-1400 nm), whereas the spectra of the radical anion species were blue-shifted (550-850 nm) compared than that of the parent 1a(•-) (550-1100 nm). The DFT computation results suggested that the radical states of lowest energy transitions occurred primarily from π to π(SOMO) or from π(SOMO) to π*. PMID:26302452

  10. 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.

  11. Lamellar versus compact self-assembly of lipoguanosine derivatives in thin surface films.

    PubMed

    Čoga, Lucija; Masiero, Stefano; Drevenšek-Olenik, Irena

    2014-09-01

    We performed a comparative study on the self-assembling properties of four guanosine derivatives with one and two lipophilic chains of two different lengths at the air-water interface and after Langmuir-Blodgett (LB) deposition onto various solid supports (mica, silicon wafer, graphite). At the air-water interface the derivatives with one lipophilic chain exhibit surface compression behaviour with a profound first order phase transition from the liquid-expanded to the liquid-condensed phase. They assemble into lamellar surface formations, whose structural characteristics remain practically unmodified after their transfer onto the solid substrates. Domain regions with orientationally aligned lamellar formations of sizes up to 150μm(2) can be obtained. The compression behaviour of double-chain derivatives is more diverse. While the derivative with two decanoyl chains exhibits the liquid-expanded as well as the liquid-condensed phase, the derivative with two hexadecanoyl chains reveals only the condensed-analogous phase with a relatively high collapse pressure. LB films of double chain derivatives show formation of very homogeneous and compact surface structures with high surface coverage. PMID:24956505

  12. Block copolymer assisted synthesis of porous α-Ni(OH)2 microflowers with high surface areas as electrochemical pseudocapacitor materials.

    PubMed

    Bastakoti, Bishnu Prasad; Huang, Hou-Sheng; Chen, Lin-Chi; Wu, Kevin C-W; Yamauchi, Yusuke

    2012-09-21

    Porous α-Ni(OH)(2) microflowers are successfully synthesized via a one-step aqueous-phase reaction assisted by block copolymers under mild conditions. The electrochemical measurement demonstrates that the α-Ni(OH)(2) microflowers calcined at 200 °C are capable to deliver a specific capacity of 1551 F g(-1) in 6 M KOH solution, suggesting their high potential as a novel electrochemical pseudocapacitor.

  13. Ratiometric electrochemical detection of alkaline phosphatase.

    PubMed

    Goggins, Sean; Naz, Christophe; Marsh, Barrie J; Frost, Christopher G

    2015-01-11

    A novel ferrocene-derived substrate for the ratiometric electrochemical detection of alkaline phosphatase (ALP) was designed and synthesised. It was demonstrated to be an excellent electrochemical substrate for the ALP-labelled enzyme-linked immunosorbent assay (ELISA).

  14. Tetrabenzoporphyrin and -mono-, -cis-di- and Tetrabenzotriazaporphyrin Derivatives: Electrochemical and Spectroscopic Implications of meso CH Group Replacement with Nitrogen.

    PubMed

    van As, Adele; Joubert, Chris C; Buitendach, Blenerhassitt E; Erasmus, Elizabeth; Conradie, Jeanet; Cammidge, Andrew N; Chambrier, Isabelle; Cook, Michael J; Swarts, Jannie C

    2015-06-01

    Nonperipherally hexyl-substituted metal-free tetrabenzoporphyrin (2H-TBP, 1a) tetrabenzomonoazaporphyrin (2H-TBMAP, 2a), tetrabenzo-cis-diazaporphyrin (2H-TBDAP, 3a), tetrabenzotriazaporphyrin (2H-TBTAP, 4a), and phthalocyanine (2H-Pc, 5a), as well as their copper complexes (1b-5b), were synthesized. As the number of meso nitrogen atoms increases from zero to four, λmax of the Q-band absorption peak becomes red-shifted by almost 100 nm, and extinction coefficients increased at least threefold. Simultaneously the blue-shifted Soret (UV) band substantially decreased in intensity. These changes were related to the relative electron-density of each macrocycle expressed as the group electronegativity sum of all meso N and CH atom groups, ∑χR. X-ray photoelectron spectroscopy differentiated between the three different types of macrocyclic nitrogen atoms (the Ninner, (NH)inner, and Nmeso) in the metal-free complexes. Binding energies of the Nmeso and Ninner,Cu atoms in copper chelates could not be resolved. Copper insertion lowered especially the cathodic redox potentials, while all four observed redox processes occurred at larger potentials as the number of meso nitrogens increased. Computational chemical methods using density functional theory confirmed 1b to exhibit a Cu(II) reduction prior to ring-based reductions, while for 2b, Cu(II) reduction is the first reductive step only if the nonperipheral substituents are hydrogen. When they are methyl groups, it is the second reduction process; when they are ethyl, propyl, or hexyl, it becomes the third reductive process. Spectro-electrochemical measurements showed redox processes were associated with a substantial change in intensity of at least two main absorbances (the Q and Soret bands) in the UV spectra of these compounds. PMID:25970004

  15. 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.

  16. 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. PMID:26799857

  17. 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.

  18. Thermal inertias in the upper millimeters of the Martian surface derived using Phobos' shadow

    NASA Technical Reports Server (NTRS)

    Betts, Bruce H.; Murray, Bruce C.; Svitek, Tomas

    1995-01-01

    The first thermal images of Phobos' shadow on the surface of Mars, in addition to simultaneous visible images, were obtained by the Phobos'88 Termoskan instrument. The best observed shadow occurrence was on the flanks of Arsia Mons. For this occurrence, we combined the observed decrease in visible illumination of the surface with the observed decrease in brightness temperature to calculate thermal inertias of the Martian surface. The most realistic of our three models of eclipse cooling improves upon our preliminary model by including nonisothermal initial conditions and downward atmospheric flux. Most of our derived inertias fall within the range 38 to 59 J/(sq m s(exp 1/2) K), (0.9 to 1.4 x 10(exp -3) cal/(sq cm s(exp 1/2) K)) corresponding to dust-sized particles (for a homogeneous surface), consistent with previous theories of Tharsis as a current area of dust deposition. Viking infrared thermal mapper (IRTM) inertias are diurnally derived and are sensitive to centimeter depths, whereas the shadow-derived inertias sample the upper tenths of a millimeter of the surface. The shadow-derived inertias are lower than those derived from Viking IRTM measurements (84 to 147), however, uncertainties in both sets of derived inertias make conclusions about layering tenuous. Thus, near-surface millimeter versus centimeter layering may exist in this region, but if it does, it is likely not very significant. Both eclipse and diurnal inertias appear to increase near the eastern end of the shadow occurrence. We also analyzed a shadow occurrence near the crater Herschel that showed no observed cooling. This analysis was limited by cool morning temperatures and instrument sensitivity, but yielded a lower bound of 80 on eclipse inertias in that region. Based upon our results, we strongly recommend future spacecraft thermal observations of Phobos' shadow, and suggest that they will be most useful if they improve upon Terinoskan's geographic and temporal coverage and its accuracy.

  19. 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

  20. 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.

  1. 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.

  2. 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. PMID:16863157

  3. 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.

  4. Effects of protonation of pyridine moieties on the 2D assembly of porphyrin layers on Au(111) at electrochemical interfaces.

    PubMed

    Yoshimoto, Soichiro

    2012-05-14

    Unique molecular assemblies of a porphyrin derivative are prepared on Au(111) by controlling the protonation/unprotonation of the pyridine groups. The porphyrin derivative, driven by the protonation of the pyridine groups, can provide characteristic assemblies with specific molecular conformations on an Au(111) surface at the electrochemical interface. In situ scanning tunneling microscopy images revealed clear differences in the adlayer structures for the unprotonated and the protonated forms of the molecules that depended upon the electrochemical potential.

  5. Surface damages in diamond by Ar/O{sub 2} plasma and their effect on the electrical and electrochemical characteristics of boron-doped layers

    SciTech Connect

    Denisenko, A.; Pietzka, C.; Scharpf, J.; Kohn, E.; Romanyuk, A.

    2010-10-15

    Epitaxial single crystal and boron-doped diamond layers were exposed to reactive ion etching in Ar/O{sub 2} plasma (rf power of 25 W and self-bias of 100 V); and the electrical, structural, and electrochemical characteristics of the exposed surface were investigated. Angle-resolved x-ray photoemission spectroscopy (XPS) measurements revealed a nonuniform layer of amorphous carbon at the exposed surface with an average thickness of approximately 4 nm, as confirmed also by atomic force microscopy profiling of selectively etched areas. On highly boron-doped diamond, the plasma-induced damages resulted also in a nonconductive surface layer. This damaged and insulating surface layer remained resistant to graphite-etching chemicals and to rf oxygen plasma but it was removed completely in microwave hydrogen plasma at 700 deg. C. The surface characteristics after the H-plasma process followed by wet chemical oxidation were restored back to the initial state, as confirmed by XPS. Such ''recovery'' treatment had been applied to an all-diamond submicrometer electrode array initially patterned by an Ar/O{sub 2} plasma etching. The electrochemical characteristics of this electrode array were improved by more than two orders of magnitude, approaching theoretical limit for the given geometrical configuration.

  6. Techniques Deriving Land Cover and Earth Surface Deformation Information from Polarimetric SAR Interferometry- Final Report

    NASA Astrophysics Data System (ADS)

    Pottier, E.; Chen, E.; Li, Z.; Hong, W.; Xiang, M.; Li, Y.; Cloude, S. R.; Papathanassiou, K.; Zhang, L.; Li, X.

    2013-01-01

    In this paper we provide a summary of activities carried out under the DRAGON collaborative program in a project concerned with the application of Pol-InSAR to deriving land cover and Earth Surface deformation information. This project (ID. 5344) is based around four main scientific topics: Land Cover Analysis, Earth Surface Deformation Monitoring and DEM Extraction, Forest Vertical Structure Parameters Extraction and PolSARpro Software Development.

  7. Application of Satellite-Derived Land Surface Temperature to Minimum Temperature Forecasting

    NASA Technical Reports Server (NTRS)

    Jones, P. R.; Jedlovec, G. J.; Suggs, R. J.; Haines, S. L.

    2004-01-01

    Satellite-derived land surface temperature (LST) is studied for the purpose of understanding regional skin temperature dependency and variability, and its relationship to corresponding, site-specific air temperature. Skin temperature is highly correlated with surface-air temperature although it differs depending on land surface characteristics, terrain, and atmospheric conditions on a diurnal and seasonal scale. The high temporal resolution of the Geostationary Operational Environmental Satellite (GOES) -12 sounder is used to compare the diurnal cycles of LST and surface-air temperature. The minimum for both temperatures occurs near sunrise and LST is found to agree closely with surface-air temperatures a period of hours before sunrise on clear sky nights. The Moderate Resolution Imaging Spectroradiometer (MODIS)-derived LST renders more horizontal temperature structure - with its high spatial resolution (1 km at nadir) compared to the GOES-12 sounder (10 km). Nighttime MODIS-derived LST is extrapolated to the time of minimum temperature for a number of case study days and these are grouped by season and atmospheric conditions. These composites show that the variation in LST mirror the variation in minimum surface-air temperature under similar conditions.

  8. 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

  9. The evaluation of surface diffusion coefficients of gold and platinum atoms at electrochemical interfaces from combined STM-SEM imaging and electrochemical techniques

    SciTech Connect

    Alonso, C.; Salvarezza, R.C.; Vara, J.M.; Arvia, A.J. ); Vazquez, L.; Bartolome, A.; Baro, A.M. )

    1990-07-01

    A simple method is presented for measuring the surface diffusion coefficients of Au and Pt atoms at electrodispersed electrodes of the same metals in contact with 0.5{ital M} H{sub 2}SO{sub 4}. The technique is based upon the time dependence of the surface roughness factor of electrodispersed metal overlayers. The method requires a model for the surface roughness of the metal structure. The model is deduced from microscopic measurements by a STM integrated into a conventional SEM microscope. This allows the relationship between the roughness factor and the area of the surface structure to be obtained. For Au and Pt in contact with an electrolyte solution, the values of our diffusion coefficients are higher than those reported in vacuum at the same temperature.

  10. Hierarchical porous carbon microspheres derived from porous starch for use in high-rate electrochemical double-layer capacitors.

    PubMed

    Du, Si-Hong; Wang, Li-Qun; Fu, Xiao-Ting; Chen, Ming-Ming; Wang, Cheng-Yang

    2013-07-01

    Porous starch was used as a precursor for hierarchical porous carbon microspheres. The preparation consisted of stabilisation, carbonisation and KOH activation, and the resultant hierarchical porous carbon microspheres had a large BET surface area of 3251 m(2)g(-1). Due to the large surface area and the hierarchical pore structure, electrodes made of the hierarchical porous carbon microsphere materials had high specific capacitances of 304 Fg(-1) at a current density of 0.05 Ag(-1) and 197 Fg(-1) at a current density of 180 Ag(-1) when used in a symmetric capacitor with 6M KOH as the electrolyte. After 10,000 cycles, the capacitor still exhibited a stable performance with a capacitance retention of 98%. These results indicate that porous starch is an excellent precursor to prepare high performance electrode materials for EDLCs.

  11. 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.

  12. Oriented Immobilization of His-Tagged Protein on a Redox Active Thiol Derivative of DPTA-Cu(II) Layer Deposited on a Gold Electrode—The Base of Electrochemical Biosensors

    PubMed Central

    Mikuła, Edyta; Sulima, Magdalena; Marszałek, Ilona; Wysłouch-Cieszyńska, Aleksandra; Verwilst, Peter; Dehaen, Wim; Radecki, Jerzy; Radecka, Hanna

    2013-01-01

    This paper concerns the development of an electrochemical biosensor for the determination of Aβ16–23′ and Aβ1–40 peptides. The His-tagged V and VC1 domains of Receptor for Advanced Glycation end Products (RAGE) immobilized on a gold electrode surface were used as analytically active molecules. The immobilization of His6–RAGE domains consists of: (i) formation of a mixed layer of N-acetylcysteamine (NAC) and the thiol derivative of pentetic acid (DPTA); (ii) complexation of Cu(II) by DPTA; (iii) oriented immobilization of His6–RAGE domains via coordination bonds between Cu(II) sites from DPTA–Cu(II) complex and imidazole nitrogen atoms of a histidine tag. Each modification step was controlled by cyclic voltammetry (CV), Osteryoung square-wave voltammetry (OSWV), and atomic force microscopy (AFM). The applicability of the proposed biosensor was tested in the presence of human plasma, which had no influence on its performance. The detection limits for Aβ1–40 determination were 1.06 nM and 0.80 nM, in the presence of buffer and human plasma, respectively. These values reach the concentration level of Aβ1–40 which is relevant for determination of its soluble form in human plasma, as well as in brain. This indicates the promising future application of biosensor presented for early diagnosis of neurodegenerative diseases. PMID:24005034

  13. Carbohydrate polymers as constituents of exopolymer substances in seawater, their complexing properties towards copper ions, surface and catalytic activity determined by electrochemical methods.

    PubMed

    Plavšić, Marta; Strmečki, Slađana

    2016-01-01

    The goal of this study was to investigate to which extent polysaccharides (PS) contribute to the complexing capacity for copper ion (LT), to determine their property of surface activity and evaluate their capability to cause the catalytic hydrogen evolution wave (peak "H") due to their adsorption and the catalytic groups in their structure. Complexing capacities and apparent stability constants (Kapp) were measured electrochemically for model polysaccharides (PS): carrageenans (κ-, ι- and λ-), chondroitin sulfate, dextran, dextran sulfate, Na-alginate and humic material. Cu-complexing capacities were determined for Na-alginate (logKapp=8.32) and chondroitin sulphate (logKapp=8.14). PS adsorb on different surfaces due to their amphyphylic properties and on that way they could increase the interaction of copper ions with these surfaces by forming the surface complexes with Cu ions. PMID:26453850

  14. In situ electrochemical-transmission surface plasmon resonance spectroscopy for poly(pyrrole-3-carboxylic acid) thin-film-based biosensor applications.

    PubMed

    Janmanee, Rapiphun; Baba, Akira; Phanichphant, Sukon; Sriwichai, Saengrawee; Shinbo, Kazunari; Kato, Keizo; Kaneko, Futao

    2012-08-01

    In this study, we describe the combination of transmission surface plasmon resonance (TSPR) and electrochemical techniques for the application to biosensors with conducting polymers. Electropolymerization was employed to construct poly(pyrrole-3-carboxylic acid) (PP3C) film on a gold-coated grating substrate using pyrrole-3-carboxylic acid (P3C) monomer solution in 0.5 M H(2)SO(4). In situ electrochemical-transmission surface plasmon resonance (EC-TSPR) measurements were carried out to study the kinetic and electroactivity properties of PP3C film. Immobilization of antihuman IgG on the activated surface and the binding process of human IgG and antihuman IgG in neutral solution could be detected in situ by EC-TSPR measurement. The surface modification steps on the PP3C layer led to an increase in intensity of the transmission peak. The performance, sensitivity, and utility of EC-TSPR spectroscopy showed obvious advantages for the detection of binding process with the simple experimental setup, and could be applied to the study of biomolecular interactions in various systems.

  15. 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. PMID:25064465

  16. 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.

  17. 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. PMID:27488352

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. Scanning tunneling microscopy and electrochemical study of the surface structure of Pt(10,10,9) and Pt(11,10,10) electrodes prepared under different cooling conditions

    NASA Astrophysics Data System (ADS)

    Herrero, Enrique; Orts, José M.; Aldaz, Antonio; Feliu, Juan M.

    1999-10-01

    The effect of three surface electrochemical preparation techniques for single crystal surfaces on two platinum stepped surfaces [Pt(10,10,9) and Pt(11,10,10)] has been investigated by scanning tunneling microscopy and cyclic voltammetry. The preparation techniques consisted of a thermal treatment followed by a cooling step in (a) a hydrogen+argon atmosphere, (b) air (c) iodine vapor+air. For Pt(10,10,9) and Pt(11,10,10) surfaces, the hydrogen+argon treatment provides surfaces that have a very narrow distribution of terrace widths around the nominal value and monatomic steps. On the other hand, facetted surfaces with terrace widths and steps four to five times their nominal values are obtained when the cooling is in the presence of iodine vapor. The air treatment generates surfaces in which the terrace width is not as uniform as in the H 2+Ar case and some kink sites are created. The changes in the surface topography can be followed in the voltammetric profile of the surfaces recorded in a sulfuric acid solution.

  6. Eulerian mean surface velocity field derived by combining drifter and satellite altimeter data

    NASA Astrophysics Data System (ADS)

    Uchida, Hiroshi; Imawaki, Shiro

    2003-03-01

    Combining surface drifter and satellite altimeter data,we estimate Eulerian mean sea-surface velocity with a resolution of quarter degrees in both latitude and longitude. The Eulerian mean velocity is calculated by subtracting the altimeter-derived velocity anomaly (i.e., deviation from the temporal mean) at the time when a drifter measured the surface velocity, from this drifter-measured velocity. The method is applied to the surface flow of the North Pacific, using TOPEX/POSEIDON and ERS-1/2 altimeter data, and WOCE-TOGA surface drifter data obtained during October 1992 to January 2001. The estimated Eulerian mean velocities for the Kuroshio south of Japan and the Kuroshio Extension region tend to be smaller than simple averages of drifter-derived velocities by 20 to 50 cm sec-1. The instantaneous velocities are obtained every ten days as sums of the Eulerian mean velocities and velocity anomalies. They agree well with in situ surface velocities measured by acoustic Doppler current profilers.

  7. 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.

  8. Improving evapotranspiration in a land surface model using biophysical variables derived from MSG/SEVIRI satellite

    NASA Astrophysics Data System (ADS)

    Ghilain, N.; Arboleda, A.; Sepulcre-Cantò, G.; Batelaan, O.; Ardö, J.; Gellens-Meulenberghs, F.

    2012-08-01

    Monitoring evapotranspiration over land is highly dependent on the surface state and vegetation dynamics. Data from spaceborn platforms are desirable to complement estimations from land surface models. The success of daily evapotranspiration monitoring at continental scale relies on the availability, quality and continuity of such data. The biophysical variables derived from SEVIRI on board the geostationary satellite Meteosat Second Generation (MSG) and distributed by the Satellite Application Facility on Land surface Analysis (LSA-SAF) are particularly interesting for such applications, as they aimed at providing continuous and consistent daily time series in near-real time over Africa, Europe and South America. In this paper, we compare them to monthly vegetation parameters from a database commonly used in numerical weather predictions (ECOCLIMAP-I), showing the benefits of the new daily products in detecting the spatial and temporal (seasonal and inter-annual) variability of the vegetation, especially relevant over Africa. We propose a method to handle Leaf Area Index (LAI) and Fractional Vegetation Cover (FVC) products for evapotranspiration monitoring with a land surface model at 3-5 km spatial resolution. The method is conceived to be applicable for near-real time processes at continental scale and relies on the use of a land cover map. We assess the impact of using LSA-SAF biophysical variables compared to ECOCLIMAP-I on evapotranspiration estimated by the land surface model H-TESSEL. Comparison with in-situ observations in Europe and Africa shows an improved estimation of the evapotranspiration, especially in semi-arid climates. Finally, the impact on the land surface modelled evapotranspiration is compared over a north-south transect with a large gradient of vegetation and climate in Western Africa using LSA-SAF radiation forcing derived from remote sensing. Differences are highlighted. An evaluation against remote sensing derived land surface temperature

  9. Surface-enhanced Raman spectroscopy of cadmium sulfide/cadmium selenide superlattices formed on gold by electrochemical atomic-layer epitaxy

    NASA Astrophysics Data System (ADS)

    Zou, Shouzhong; Weaver, Michael J.

    1999-10-01

    The phonon properties of ultrathin CdS/CdSe superlattice films formed on gold by electrochemical atomic-layer epitaxy are characterized by means of surface-enhanced Raman spectroscopy (SERS). Substantial (15-25 cm -1) red-shifts in the CdS phonon frequencies are observed, whereas the CdSe frequencies are essentially unaltered, indicating that substantial crystallographic strain occurs in the former, but not the latter, superlattice component. The findings demonstrate the virtues of SERS for exploring the structure of such solid-solid interfaces with unique monolayer-level sensitivity.

  10. How well Can We Classify SWOT-derived Water Surface Profiles?

    NASA Astrophysics Data System (ADS)

    Frasson, R. P. M.; Wei, R.; Picamilh, C.; Durand, M. T.

    2015-12-01

    The upcoming Surface Water Ocean Topography (SWOT) mission will detect water bodies and measure water surface elevation throughout the globe. Within its continental high resolution mask, SWOT is expected to deliver measurements of river width, water elevation and slope of rivers wider than ~50 m. The definition of river reaches is an integral step of the computation of discharge based on SWOT's observables. As poorly defined reaches can negatively affect the accuracy of discharge estimations, we seek strategies to break up rivers into physically meaningful sections. In the present work, we investigate how accurately we can classify water surface profiles based on simulated SWOT observations. We assume that most river sections can be classified as either M1 (mild slope, with depth larger than the normal depth), or A1 (adverse slope with depth larger than the critical depth). This assumption allows the classification to be based solely on the second derivative of water surface profiles, with convex profiles being classified as A1 and concave profiles as M1. We consider a HEC-RAS model of the Sacramento River as a representation of the true state of the river. We employ the SWOT instrument simulator to generate a synthetic pass of the river, which includes our best estimates of height measurement noise and geolocation errors. We process the resulting point cloud of water surface heights with the RiverObs package, which delineates the river center line and draws the water surface profile. Next, we identify inflection points in the water surface profile and classify the sections between the inflection points. Finally, we compare our limited classification of simulated SWOT-derived water surface profile to the "exact" classification of the modeled Sacramento River. With this exercise, we expect to determine if SWOT observations can be used to find inflection points in water surface profiles, which would bring knowledge of flow regimes into the definition of river reaches.

  11. 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.

  12. Evidence for the intrinsic nature of band-gap states electrochemically observed on atomically flat TiO2(110) surfaces.

    PubMed

    Takata, Shintaro; Miura, Yoshihiro; Matsumoto, Yuji

    2014-12-01

    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.

  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. Electrochemical and surface spectroscopic studies of thin films of bismuth ruthenium oxide (Bi{sub 2}Ru{sub 2}O{sub 7})

    SciTech Connect

    Wideloev, A.; Markovic, N.M.; Ross, P.N. Jr.

    1996-11-01

    Thin, nonporous films of bismuth ruthenium oxide having the pyrochlore crystal structure were prepared by ion beam deposition. The films were grown on metal disks machined to fit into a rotating ring-disk electrode. The electrocatalytic properties of these films for O{sub 2} reduction and evolution were studied in 1 M KOH using the rotating ring-disk electrode method in conjunction with spectroscopic studies of the surfaces before and after electrochemical analysis. The crystalline pyrochlore film was found to be an extremely poor oxygen reduction catalyst, but it could be activated in situ by a procedure that created a highly porous amorphous structure by dissolution of bismuth cations into the solution. The authors found in separate experiments that bismuth ions in solution increased the oxygen reduction activity of a nonporous ruthenium oxide surface, and suggest that there is an analogous effect on the activity of the residual, ruthenium-rich oxide surface by bismuth ions in solution following activation.

  15. 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

  16. Deriving New Topography-based Global Datasets for Land Surface Modeling

    NASA Astrophysics Data System (ADS)

    Tesfa, T. K.; Leung, L. R.

    2015-12-01

    Topography exerts a major control on land surface processes through its influence on atmospheric forcing, soil and vegetation properties, network topology and drainage area. Land surface spatial structure that captures spatial heterogeneity influenced by topography is expected to improve representation of land surface processes in land surface models. For example, land surface modeling using subbasins instead of regular grids as computational units has demonstrated improved scalability of simulated runoff and streamflow processes. In this study, a local classification method is applied to derive a new land surface spatial structure defined by further dividing subbasins into subgrid units based on elevation, topographic slope and aspect to take advantage of the emergent patterns and scaling properties of atmospheric, hydrologic, and vegetation processes in land surface models. For this purpose, a more consistent 90 meter resolution global surface elevation data has been developed by blending elevation data obtained from various sources. Taking the advantage of natural hydrologic connectivity of watersheds, new subbasin-based river routing and reservoir dependency datasets are being developed to improve representation of the managed hydrologic systems in the Community Land Model.

  17. 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.

  18. Electrochemical properties of honeycomb-like structured HFBI self-organized membranes on HOPG electrodes.

    PubMed

    Yamasaki, Ryota; Takatsuji, Yoshiyuki; Lienemann, Michael; Asakawa, Hitoshi; Fukuma, Takeshi; Linder, Markus; Haruyama, Tetsuya

    2014-11-01

    HFBI (derived from Trichoderma sp.) is a unique structural protein, which forms a self-organized monolayer at both air/water interface and water/solid interfaces in accurate two-dimensional ordered structures. We have taken advantage of the unique functionality of HFBI as a molecular carrier for preparation of ordered molecular phase on solid substrate surfaces. The HFBI molecular carrier can easily form ordered structures; however, the dense molecular layers form an electrochemical barrier between the electrode and solution phase. In this study, the electrochemical properties of HFBI self-organized membrane-covered electrodes were investigated. Wild-type HFBI has balanced positive and negative charges on its surface. Highly oriented pyrolytic graphite (HOPG) electrodes coated with HFBI molecules were investigated electrochemically. To improve the electrochemical properties of this HFBI-coated electrode, the two types of HFBI variants, with oppositely charged surfaces, were prepared genetically. All three types of HFBI-coated HOPG electrode perform electron transfer between the electrode and solution phase through the dense HFBI molecular layer. This is because the HFBI self-organized membrane has a honeycomb-like structure, with penetrating holes. In the cases of HFBI variants, the oppositely charged HFBI membrane phases shown opposite electrochemical behaviors in electrochemical impedance spectroscopy. HFBI is a molecule with a unique structure, and can easily form honeycomb-like structures on solid material surfaces such as electrodes. The molecular membrane phase can be used for electrochemical molecular interfaces.

  19. 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.

  20. 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.

  1. 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.

  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. Resolving the diurnal cycle in satellite derived sea surface temperatures and its significance on surface heat fluxes

    NASA Astrophysics Data System (ADS)

    Weihs, R. R.; Bourassa, M. A.

    2010-12-01

    Marine surface heat fluxes across the globe need to be resolved on a smaller time scale in order to determine how changes in their diurnal cycle contribute to surface turbulent fluxes. In order to do this, the sea surface temperatures used to calculate the fluxes also need to accurately represent diurnal changes. Since most satellite derived sea surface temperature products are time-averaged and smoothed so that intradiurnal variations are neglected, and insitu measurements are scarce in global spatial coverage, modeling of the diurnal cycle of SSTs becomes necessary. A bulk flux model, POSH (Gentemann et al. 2009), will be used to calculate a global field of diurnally varying sea surface temperatures (dSSTs) over the course of 2 months in two different annual seasons, winter and summer. As the model produces a dSST field, surface turbulent heat fluxes are calculated using the Bourassa (2006) flux model. In order to compute fluxes, bulk atmospheric variables are taken from the MERRA (Modern Era Retrospective-Analysis for Research and Applications) reanalysis dataset. Sea surface temperatures are obtained from the AVHRR-only Reynolds Daily OI Sea Surface Temperature product (Reynolds et al. 2007). The Reynolds SST is bias-corrected relative to a 7-day in-situ SST so therefore it does not resolve the diurnal cycle itself. The Reynolds SST product will serve as a foundation temperature, or the temperature that is independent from the effects of diurnal heating (Donolan et al. 2007), of which the amplitude of the diurnal heating will be added to. Finally, 2-monthly average differences in dSSTs versus Daily OI SSTs and uncertainties in the biases will be compared. From these statistics, climactic and modeling significance of the inclusion of diurnal heating can be evaluated. We find that latent heat fluxes in the tropics are increased by roughly 10 Wm-2 when the diurnal variability is considered (Fig. 1). This change in flux decreases poleward. The tropical changes are

  4. The inaccuracy of surface-measured model-derived tibiofemoral kinematics.

    PubMed

    Li, Kang; Zheng, Liying; Tashman, Scott; Zhang, Xudong

    2012-10-11

    This study assessed the accuracy of surface-measured OpenSim-derived tibiofemoral kinematics in functional activities. Ten subjects with unilateral, isolated grade II PCL deficiency performed level running and stair ascent. A dynamic stereo radiography (DSX) system and a Vicon motion capture system simultaneously measured their knee or lower extremity movement. Surface marker motion data from the Vicon system were used to create subject-specific models in OpenSim and derive the tibiofemoral kinematics. The surface-measured model-derived tibiofemoral kinematics in all six degrees of freedom (DOFs) were then compared with those measured by the DSX as the benchmarks. The differences between surface- and DSX-measured tibiofemoral kinematics were found to be substantial: the overall mean (±SD) RMS differences during running were 9.1±3.2°, 2.0±1.2°, and 6.4±4.5° for the flexion-extension, abduction-adduction, and internal-external rotations, respectively, and 7.1±3.2 mm, 8.8±3.7 mm, and 1.9±1.2 mm for anterior-posterior, proximal-distal, and medial-lateral translations, respectively. The differences were more pronounced in relatively higher speed running than in stair ascent. It was also found that surface-based measures significantly underestimated the mean as well as inter-subject variability of the differences between PCL-injured and intact knees in abduction-adduction, internal-external rotations, and anterior-posterior translation.

  5. Cell attachment and proliferation of bone marrow-derived osteoblast on zirconia of various surface treatment

    PubMed Central

    Lee, Heesu; Noh, Kwantae; Woo, Yi-Hyung

    2014-01-01

    PURPOSE This study was performed to characterize the effects of zirconia coated with calcium phosphate and hydroxyapatite compared to smooth zirconia after bone marrow-derived osteoblast culture. MATERIALS AND METHODS Bone marrow-derived osteoblasts were cultured on (1) smooth zirconia, (2) zirconia coated with calcium phosphate (CaP), and (3) zirconia coated with hydroxyapatite (HA). The tetrazolium-based colorimetric assay (MTT test) was used for cell proliferation evaluation. Scanning electron microscopy (SEM) and alkaline phosphatase (ALP) activity was measured to evaluate the cellular morphology and differentiation rate. X-ray photoelectron spectroscopy (XPS) was employed for the analysis of surface chemistry. The genetic expression of the osteoblasts and dissolution behavior of the coatings were observed. Assessment of the significance level of the differences between the groups was done with analysis of variance (ANOVA). RESULTS From the MTT assay, no significant difference between smooth and surface coated zirconia was found (P>.05). From the SEM image, cells on all three groups of discs were sporadically triangular or spread out in shape with formation of filopodia. From the ALP activity assay, the optical density of osteoblasts on smooth zirconia discs was higher than that on surface treated zirconia discs (P>.05). Most of the genes related to cell adhesion showed similar expression level between smooth and surface treated zirconia. The dissolution rate was higher with CaP than HA coating. CONCLUSION The attachment and growth behavior of bone-marrow-derived osteoblasts cultured on smooth surface coated zirconia showed comparable results. However, the HA coating showed more time-dependent stability compared to the CaP coating. PMID:24843393

  6. 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.

  7. Electrochemical synthesis on single cells as templates.

    PubMed

    Tam, Jasper; Salgado, Shehan; Miltenburg, Mark; Maheshwari, Vivek

    2013-10-01

    The cell surface is made electrochemically active by interfacing with graphene sheets. The electrical and thermal properties of graphene allow the control of cell surface potential for electrochemical synthesis. Using this approach radially projecting ZnO nanorods are templated on the surface of single cells. This reported single cell photosensor has superior performance than similar devices made on planar surfaces.

  8. 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...

  9. 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.

  10. Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface-Immobilized Copper Thioether Clip-Phen Derivative.

    PubMed

    Romo, Adolfo I B; Abreu, Dieric S; de F Paulo, Tércio; Carepo, Marta S P; Sousa, Eduardo H S; Lemus, Luis; Aliaga, Carolina; Batista, Alzir A; Nascimento, Otaciro R; Abruña, Héctor D; Diógenes, Izaura C N

    2016-07-11

    Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip-phen derivative, 1,3-bis(1,10-phenanthrolin-2-yloxy)-N-(4-(methylthio)benzylidene)propan-2-amine (2CP-Bz-SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu(I) intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H2 O2 , thus pointing to a mechanism involving a Fenton-like reaction that results in the production of OH(.) .

  11. Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface-Immobilized Copper Thioether Clip-Phen Derivative.

    PubMed

    Romo, Adolfo I B; Abreu, Dieric S; de F Paulo, Tércio; Carepo, Marta S P; Sousa, Eduardo H S; Lemus, Luis; Aliaga, Carolina; Batista, Alzir A; Nascimento, Otaciro R; Abruña, Héctor D; Diógenes, Izaura C N

    2016-07-11

    Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip-phen derivative, 1,3-bis(1,10-phenanthrolin-2-yloxy)-N-(4-(methylthio)benzylidene)propan-2-amine (2CP-Bz-SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu(I) intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H2 O2 , thus pointing to a mechanism involving a Fenton-like reaction that results in the production of OH(.) . PMID:27310653

  12. Measurement of surface resistivity/conductivity of different organic thin films by a combination of optical shearography and electrochemical impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Habib, Khaled

    2013-11-01

    Shearography techniques were applied again to measure the surface resistivity/conductivity of different organic thin films on a metallic substrate. The coatings were ACE premium-grey enamel (spray coating), a yellow Acrylic lacquer, and a gold nail polish on a carbon steel substrate. The investigation was focused on determining the in-plane displacement of the coatings by shearography between 20 and 60 °C. Then, the alternating current (AC) impedance (resistance) of the same coated samples was determined by electrochemical impedance spectroscopy (EIS) in 3.0% NaCl solution at room temperature. As a result, the proportionality constant (resistivity or conductivity = 1/surface resistivity) between the determined AC impedance and the in-plane displacement was obtained. The obtained resistivity of all investigated coatings, 40:15 × 106-24:6 × 109Ωcm, was found in the insulator range.

  13. Functionalized gold nanoparticle-polypyrrole nanobiocomposite with high effective surface area for electrochemical/pH dual stimuli-responsive smart release of insulin.

    PubMed

    Shamaeli, Ehsan; Alizadeh, Naader

    2015-02-01

    A novel functionalized gold nanoparticle-polypyrrole-nanobiocomposite (PPy-FGNP-NBC) with large effective surface area was fabricated for electrical/pH dual stimuli-responsive local delivery of insulin. The fabrication method involves simple electrodeposition and immobilization processes without use of organic solvents. Release studies based on the nature of insulin-surface binding indicated that release was promoted for PPy-FGNP-NBC. Kinetics analysis showed that release of insulin strongly affected by applying external potential stimuli. Also, the insulin release was under influence of pH and was slowed down under lower pH. This pH-sensitivity was remarkably increased by applying potential. Based on in vitro release study under applied potential condition, insulin release in the artificial gastric juice is significantly slower than that in the artificial intestinal fluid. Circular dichroism analysis showed that insulin retained its original conformation during electrochemically stimulated release.

  14. 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

  15. 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.

  16. Improved electrochemical and thermal performances of layered Li[Li0.2Ni0.17Co0.07Mn0.56]O2 via Li2ZrO3 surface modification

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoping; Sun, Shuwei; Wu, Qing; Wan, Ning; Pan, Du; Bai, Ying

    2015-05-01

    A conductive Li2ZrO3 layer is successfully coated on the surface of Li-rich layered cathode Li[Li0.2Ni0.17Co0.07Mn0.56]O2 to enhance its electrochemical performances. The crystal structures, electrochemical properties and thermal stabilities of the bare and coated materials are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), electron diffraction spectroscopy (EDS), inductively coupled plasma (ICP), galvanostatic cycling, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). It has been found that the electrochemical performances of Li-rich cathode material are obviously improved by Li2ZrO3 surface modification. Especially, the 1 wt.% Li2ZrO3-coated material demonstrates the best cycling performance, with capacity retention of 89% after 50 cycles, much better than that of the pristine one, 64%. Intensive explorations indicate that the improved electrochemical properties can be attributed to the Li2ZrO3 surface layer, which not only stabilizes the cathode structure by decreasing the loss of oxygen, but also protects the Li-rich cathode material from side reaction(s) with the electrolyte and thus suppressing the fast growth of solid electrolyte interface (SEI) film on the surface of oxide particles.

  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. Electrochemistry of ferrocene derivatives on highly oriented pyrolytic graphite (HOPG): quantification and impacts of surface adsorption.

    PubMed

    Cuharuc, Anatolii S; Zhang, Guohui; Unwin, Patrick R

    2016-02-14

    Cyclic voltammetry of three ferrocene derivatives - (ferrocenylmethyl)trimethylammonium (FcTMA(+)), ferrocenecarboxylic acid (FcCOOH), and ferrocenemethanol (FcCH2OH) - in aqueous solutions shows that the reduced form of the first two redox species weakly adsorbs onto freshly cleaved surfaces of highly oriented pyrolytic graphite (HOPG), with the fractional surface coverage being in excess of 10% of a monolayer at a bulk concentration level of 0.25 mM for both compounds. FcCH2OH was found to exhibit greater and stronger adsorption (up to a monolayer) for the same bulk concentration. The adsorption of FcTMA(+) on freshly cleaved surfaces of high quality (low step edge density) and low quality (high step edge density) HOPG is the same within experimental error, suggesting that the amount of step edges has no influence on the adsorption process. The amount of adsorption of FcTMA(+) is the same (within error) for low quality HOPG, irrespective of whether the surface is freshly cleaved or left in air for up to 12 hours, while - with aging - high quality HOPG adsorbs notably more FcTMA(+). The formation of an airborne contaminating film is proposed to be responsible for the enhanced entrapment of FcTMA(+) on aged high quality HOPG surfaces, while low quality surfaces appear less prone to the accumulation of such films. The impact of the adsorption of ferrocene derivatives on graphite for voltammetric studies is discussed. Adsorption is quantified by developing a theory and methodology to process cyclic voltammetry data from peak current measurements. The accuracy and applicability, as well as limits of the approach, are demonstrated for various adsorption isotherms.

  19. 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

  20. The derivation and verification of surface reflectances using airborne MSS data and a radiative transfer model

    SciTech Connect

    Ramsey, E.W. III; Jensen, J.R.

    1988-01-01

    Surface reflectance images were derived from airborne MSS data using a radiative transfer model to eliminate atmospheric effects and to derive downwelling irradiances. Input radiative transfer model parameters and Brightness Value (BV) to radiance conversion gain and bias factors were generated for each band using an optimization procedure to minimize the difference between modelled and image BV. Subsequently, reflectance images were derived at five wavelengths from the blue to red bands using the optimized parameters as inputs into the radiative transfer model. Modelled surface reflectance images were evaluated for accuracy by statistical comparison to measured reflectances, and for improved contrast by subjective comparison to the original images. Daedalus DS-1260 MSS bands 3, 4 and 5 modelled reflectances explained 25%, 75% and 72% of the measured reflectance variances, respectively; while bands 2 and 7 correlation were not significant (p < .05). Finally, the generated reflectance images showed dramatic improvement in contrast, revealing textures that were not apparent in the original images. 20 refs., 4 figs., 3 tabs.

  1. Structural considerations on acridine/acridinium derivatives: Synthesis, crystal structure, Hirshfeld surface analysis and computational studies

    NASA Astrophysics Data System (ADS)

    Wera, Michał; Storoniak, Piotr; Serdiuk, Illia E.; Zadykowicz, Beata

    2016-02-01

    This article describes a detailed study of the molecular packing and intermolecular interactions in crystals of four derivatives of acridine, i.e. 9-methyl-, 9-ethyl, 9-bromomethyl- and 9-piperidineacridine (1, 2, 3 and 4, respectively) and three 10-methylacridinium salts containing the trifluoromethanesulphonate anion and 9-vinyl-, 9-bromomethyl, and 9-phenyl-10-methylacridinium cations (5, 6 and 7, respectively). The crystal structures of all of the compounds are stabilized by long-range electrostatic interactions, as well as by a network of short-range C-HṡṡṡO (in hydrates and salts 3 and 5-7, respectively), C-Hṡṡṡπ, π-π, C-Fṡṡṡπ and S-Oṡṡṡπ (in salts 5-7) interactions. Hirshfeld surface analysis shows that various intermolecular contacts play an important role in the crystal packing, graphically exhibiting the differences in spatial arrangements of the acridine/acridinium derivatives under scrutiny here. Additionally, computational methods have been used to compare the intermolecular interactions in the crystal structures of the investigated compounds. Computations have confirmed the great contribution of dispersive interactions for crystal lattice stability in the case of 9-substituted acridine and electrostatic interactions for the crystal lattice stability in the case of 9-substituted 10-methylacridinium trifluoromethanesulphonates. The value of crystal lattice energy and the electrostatic contribution in the crystal lattice energy of monohydrated acridine derivatives have confirmed that these compounds have behave as acridinium derivatives.

  2. Regulatory Network Decoded from Epigenomes of Surface Ectoderm-Derived Cell Types

    PubMed Central

    Lowdon, Rebecca F.; Zhang, Bo; Bilenky, Misha; Mauro, Thea; Li, Daofeng; Gascard, Philippe; Sigaroudinia, Mahvash; Farnham, Peggy J.; Bastian, Boris C.; Tlsty, Thea D.; Marra, Marco A.; Hirst, Martin; Costello, Joseph F.; Wang, Ting; Cheng, Jeffrey B.

    2015-01-01

    Developmental history shapes the epigenome and biological function of differentiated cells. Epigenomic patterns have been broadly attributed to the three embryonic germ layers. Here we investigate how developmental origin influences epigenomes. We compare key epigenomes of cell types derived from surface ectoderm (SE), including keratinocytes and breast luminal and myoepithelial cells, against neural crest-derived melanocytes and mesoderm-derived dermal fibroblasts to identify SE differentially methylated regions (SE-DMRs). DNA methylomes of neonatal keratinocytes share many more DMRs with adult breast luminal and myoepithelial cells than with melanocytes and fibroblasts from the same neonatal skin. This suggests that SE origin contributes to DNA methylation patterning, while shared skin tissue environment has limited effect on epidermal keratinocytes. Hypomethylated SE-DMRs are in proximity to genes with SE relevant functions. They are also enriched for enhancer- and promoter-associated histone modifications in SE-derived cells, and for binding motifs of transcription factors important in keratinocyte and mammary gland biology. Thus, epigenomic analysis of cell types with common developmental origin reveals an epigenetic signature that underlies a shared gene regulatory network. PMID:25421844

  3. 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.

  4. 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.

  5. High-Performance Simulations of the Diffusion Characteristics of a Pentacene Derivative on Gold Surfaces

    NASA Astrophysics Data System (ADS)

    Miller, Ryan; Larson, Amanda; Pohl, Karsten

    Pentacene serves as a backbone for several molecules that provide attractive qualities for organic photovoltaic devices. One of these pentacene derivatives is 5 6,7-trithiapentacene-13-one (TTPO), which is unique in that it achieves its lowest energy configuration on Au(1 1 1) surfaces with the thiol group angled down towards the surface, allowing many molecules to pack closely together and form molecular nanowires. However, TTPO diffuses on flat surfaces, making it difficult for the self-assembly process to be initiated. With the help of the low-energy sites in surface defects and Au(7 8 8) step edges, TTPO molecules can be anchored in place on surfaces, allowing for chain formation to begin. By using high-performance Density Functional Theory based molecular dynamics calculations, the molecules can be shown to stay localized to these bonding sites and serve as a basis for chain formation. In addition, by simulating various temperatures with a Nose-Hoover thermostat, we can analyze how temperature affects anchoring ability and diffusion properties.

  6. Evaluation of SEBS for Deriving Land Surface Energy Fluxes with MODIS Data in a Semiarid Region

    NASA Astrophysics Data System (ADS)

    Jayanthi, H.; Gowda, P. H.; Scanlon, B. R.; Howell, T. A.; Paul, G.

    2010-12-01

    Texas High Plains is one of the largest agricultural regions in the U.S. where 90% of the water derived from the Ogallala aquifer is used for irrigation. Accurate seasonal evapotranspiration (ET) estimates at a regional scale would be useful for groundwater management purposes. Remote sensing based ET models are suitable for this purpose. The main objective of this study was to evaluate the Surface Energy Balance System (SEBS) for its ability to estimate ET using Moderate Resolution Imaging Spectroradiometer (MODIS) data. For this purpose, the SEBS was implemented with MODIS data acquired during the 2007 crop growing season. The accuracy of the 250-m MODIS ET maps was assessed using ET data derived from Landsat Thematic Mapper (TM) images that were compared and validated against lysimetric data as part of another study and upscaled to 250 m for comparison. This presentation will discuss the statistical results and evaluate the strengths and weaknesses of the SEBS model.

  7. 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

  8. 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%.

  9. Electrochemical Surface Plasmon Resonance (EC-SPR) and Waveguide Enhanced Glucose Biosensing with N-Alkylaminated Polypyrrole/Glucose Oxidase Multilayers

    PubMed Central

    Baba, Akira; Taranekar, Prasad; Ponnapati, Ramakrishna R.; Knoll, Wolfgang; Advincula, Rigoberto C.

    2010-01-01

    In this work, we report an electrochemical surface plasmon resonance/waveguide (EC-SPR/waveguide) glucose biosensor, which could detect enzymatic reactions in a conducting polymer/glucose oxidase (GOx) multilayer thin film. In order to achieve a controlled enzyme electrode and waveguide mode, GOx (negatively charged) was immobilized with a water-soluble conducting N-alkylaminated polypyrrole (positively charged) using the layer-by-layer (LbL) electrostatic self-assembly technique. The electrochemical and optical signals were simultaneously obtained from the composite LbL enzyme electrode upon addition of glucose as mediated by the electroactivity and electrochromic property of the polypyrrole layers. The signal enhancement in the EC-SPR detection is obtained by monitoring the doping-dedoping events on the polypyrrole. The real time optical signal could be distinguished between the change in the dielectric constant of the enzyme layer and other non-enzymatic reaction events such as adsorption of glucose and change of refractive index of solution. This was possible by a correlation of both the SPR mode, m=0, and m=1 mode of the waveguide in an SPR/waveguide spectroscopy experiment. PMID:20666478

  10. 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. PMID:26874112

  11. 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.

  12. The Impact of Microwave-Derived Surface Soil Moisture on Watershed Hydrological Modeling

    NASA Technical Reports Server (NTRS)

    ONeill, P. E.; Hsu, A. Y.; Jackson, T. J.; Wood, E. F.; Zion, M.

    1997-01-01

    The usefulness of incorporating microwave-derived soil moisture information in a semi-distributed hydrological model was demonstrated for the Washita '92 experiment in the Little Washita River watershed in Oklahoma. Initializing the hydrological model with surface soil moisture fields from the ESTAR airborne L-band microwave radiometer on a single wet day at the start of the study period produced more accurate model predictions of soil moisture than a standard hydrological initialization with streamflow data over an eight-day soil moisture drydown.

  13. An error covariance model for sea surface topography and velocity derived from TOPEX/POSEIDON altimetry

    NASA Technical Reports Server (NTRS)

    Tsaoussi, Lucia S.; Koblinsky, Chester J.

    1994-01-01

    In order to facilitate the use of satellite-derived sea surface topography and velocity oceanographic models, methodology is presented for deriving the total error covariance and its geographic distribution from TOPEX/POSEIDON measurements. The model is formulated using a parametric model fit to the altimeter range observations. The topography and velocity modeled with spherical harmonic expansions whose coefficients are found through optimal adjustment to the altimeter range residuals using Bayesian statistics. All other parameters, including the orbit, geoid, surface models, and range corrections are provided as unadjusted parameters. The maximum likelihood estimates and errors are derived from the probability density function of the altimeter range residuals conditioned with a priori information. Estimates of model errors for the unadjusted parameters are obtained from the TOPEX/POSEIDON postlaunch verification results and the error covariances for the orbit and the geoid, except for the ocean tides. The error in the ocean tides is modeled, first, as the difference between two global tide models and, second, as the correction to the present tide model, the correction derived from the TOPEX/POSEIDON data. A formal error covariance propagation scheme is used to derive the total error. Our global total error estimate for the TOPEX/POSEIDON topography relative to the geoid for one 10-day period is found tio be 11 cm RMS. When the error in the geoid is removed, thereby providing an estimate of the time dependent error, the uncertainty in the topography is 3.5 cm root mean square (RMS). This level of accuracy is consistent with direct comparisons of TOPEX/POSEIDON altimeter heights with tide gauge measurements at 28 stations. In addition, the error correlation length scales are derived globally in both east-west and north-south directions, which should prove useful for data assimilation. The largest error correlation length scales are found in the tropics. Errors in

  14. Variability of basin scale water resources indicators derived from global hydrological and land surface models

    NASA Astrophysics Data System (ADS)

    Werner, Micha; Blyth, Eleanor; Schellekens, Jaap

    2016-04-01

    Global hydrological and land-surface models are becoming increasingly available, and as the resolution of these improves, as well how hydrological processes are represented, so does their potential. These offer consistent datasets at the global scale, which can be used to establish water balances and derive policy relevant indicators in medium to large basins, including those that are poorly gauged. However, differences in model structure, model parameterisation, and model forcing may result in quite different indicator values being derived, depending on the model used. In this paper we explore indicators developed using four land surface models (LSM) and five global hydrological models (GHM). Results from these models have been made available through the Earth2Observe project, a recent research initiative funded by the European Union 7th Research Framework. All models have a resolution of 0.5 arc degrees, and are forced using the same WATCH-ERA-Interim (WFDEI) meteorological re-analysis data at a daily time step for the 32 year period from 1979 to 2012. We explore three water resources indicators; an aridity index, a simplified water exploitation index; and an indicator that calculates the frequency of occurrence of root zone stress. We compare indicators derived over selected areas/basins in Europe, Colombia, Southern Africa, the Indian Subcontinent and Australia/New Zealand. The hydrological fluxes calculated show quite significant differences between the nine models, despite the common forcing dataset, with these differences reflected in the indicators subsequently derived. The results show that the variability between models is related to the different climates types, with that variability quite logically depending largely on the availability of water. Patterns are also found in the type of models that dominate different parts of the distribution of the indicator values, with LSM models providing lower values, and GHM models providing higher values in some

  15. Surface work function of chemically derived graphene: A first-principles study

    NASA Astrophysics Data System (ADS)

    Jiao, N.; He, Chaoyu; Zhou, P.; Zhang, C. X.; Xiao, H. P.; Sun, L. Z.

    2013-10-01

    Using first-principles calculations within the framework of density-functional theory, we systematically study the modulation effect of chemical decoration including hydrogenation, fluorination, and oxidization on the surface work function of graphene. The chemical decoration is effective approach to modulate the surface work function, which expands the space to design diverse nano-devices based on graphene. Moreover, we also find some un-expectation chemically decorated cases which do not follow the traditional rule of “electronegative (electropositive) adsorbates, which increase (decrease) the work function of the surface”. Such a phenomenon is mainly derived from the charge redistribution induced by the bonding process between adsorbates and carbon atoms along with the chemical decoration.

  16. Estimates of surface roughness derived from synthetic aperture radar (SAR) data

    NASA Technical Reports Server (NTRS)

    Evans, Diane L.; Farr, Tom G.; Van Zyl, Jakob J.

    1992-01-01

    Radar remote sensing data provide a unique perspective of the earth's crust and the processes that have influenced its evolution. Physically based models are required, however, to relate the geophysical quantities being measured by the radar sensor to useful geologic information. In this study, synthetic aperture radar (SAR) data over the Cima volcanic field in the Mojave Desert of California are quantitatively connected with microtopography through inversion of a radar backscatter model. Changes in surface roughness inferred from the derived microtopography are modeled and found to be consistent with aeolian mantling as surfaces age. Estimated rates of aeolian deposition for the Cima area are compared to the Lunar Crater volcanic field in Nevada. Rates of deposition appear to be higher at Cima volcanic field, most likely because of its proximity to Soda Lake, the main source of the aeolian material.

  17. 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.

  18. Selective electrochemical discrimination between dopamine and phenethylamine-derived psychotropic drugs using electrodes modified with an acyclic receptor containing two terminal 3-alkoxy-5-nitroindazole rings.

    PubMed

    Doménech, Antonio; Navarro, Pilar; Arán, Vicente J; Muro, Beatriz; Montoya, Noemí; García-España, Enrique

    2010-06-01

    Electrochemical discrimination between dopamine and psychotropic drugs which have in common a skeletal structure of phenethylamine, can be obtained using acyclic receptors L(1) and L(2), containing two terminal 3-alkoxy-5-nitroindazole rings. Upon attachment to graphite electrodes, L(1) and L(2) exhibit a well-defined, essentially reversible solid state electrochemistry in contact with aqueous media, based on electrolyte-assisted reduction processes involving successive cation and anion insertion/binding. As a result, a distinctive, essentially Nernstian electrochemical response is obtained for phenethylammonium ions of methamphetamine (METH), p-methoxyamphetamine (PMA), amphetamine (AMPH), mescaline (MES), homoveratrylamine (HOM), phenethylamine (PEA) and dopamine (DA) in aqueous media.

  19. Effect of Vegetation Patterns on SAR derived Surface Soil Moisture Distribution

    NASA Astrophysics Data System (ADS)

    Koyama, C. N.; Schneider, K.

    2012-12-01

    conditions, are used to derive biomass information independently from the soil moisture retrieval. Nevertheless, the canopy still has an attenuation effect on the co-polarized backscattering, but this can be corrected by using the vegetation information obtained from the other SAR observables. For constant permittivity states of the soil surface the canopy can have a disturbing effect of up to 6dB. This is the same order of magnitude of dynamic range as observed for soil moisture values ranging from 10 - 40 Vol.-% over bare surfaces. The present study is focused on the Rur catchment (Germany) where the effect of different vegetation patterns on the spatial distribution of near-surface soil water content is investigated by comparison between ALOS PALSAR derived biomass and soil moisture maps. The findings show that the impact of vegetation on the near-surface moisture contents may vary considerably. For wet and intermediate soil conditions where enough water is available for transpiration it was observed that the near-surface moisture content tends to be higher on vegetated fields. This may be explained by the fact that the canopy hampers evaporations due to lack of air movement while the plants uptake water from deeper soil layers. However if the water supply is low the plant water consumption can also lead to accelerated drying of the soil surface. This was especially observed for cereal crops.

  20. A novel approach for preparation of modified-biochar derived from marine macroalgae: Dual purpose electro-modification for improvement of surface area and metal impregnation.

    PubMed

    Jung, Kyung-Won; Hwang, Min-Jin; Jeong, Tae-Un; Ahn, Kyu-Hong

    2015-09-01

    In the present study, an aluminum electrode-based electrochemical process was newly adopted as a modification method for fabricating physically and chemically modified biochar derived from marine macroalgae. Specifically, a current density of 93.96 mA cm(-2) was applied for 5 min at pH 3.0. Subsequently, the mixture was stirred continuously for 30 min without electric field, and the dried sample was then pyrolyzed at 450 °C under a N2 environment for 2 h. SEM-EDS and XRD analyses clearly indicated that nano-sized aluminum crystals (beohemite, AlOOH) were uniformly present on the EM-biochar surface. Adsorption equilibrium tests showed that the phosphate adsorption onto EM-biochar agreed well with the Langmuir-Freundlich adsorption isotherm model, with a maximum adsorption capacity of 31.28 mg-P g(-1). These findings suggest that this novel and simple electro-modification method is a reasonable and effective option for simultaneously upgrading both the surface area and chemical properties of biochar.

  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. Global surface solar irradiance product derived from SCIAMACHY FRESCO cloud fraction

    NASA Astrophysics Data System (ADS)

    Wang, Ping; Stammes, Piet; Müller, Richard

    The FRESCO cloud retrieval algorithm has been developed as a simple but fast and efficient algorithm for GOME and SCIAMACHY (Koelemeijer et al., 2001; Fournier et al., 2006; Wang et al., 2008). FRESCO employs the O2 A band at 760 nm to retrieve the effective cloud fraction and cloud pressure using a simple Lambertian cloud model. The effective cloud fraction is a combination of geometric cloud fraction and cloud optical thickness, which yield the same reflectance at the top of the atmosphere as the cloud in the scene. It is well-known that clouds reduce the surface solar irradiance. Therefore the all-sky irradiance can be derived from the clear-sky irradiance with a scaling factor related to the cloud index. The cloud index is very similar to the effective cloud fraction by definition. The MAGIC (Mesoscale Atmospheric Global Irradiance Code) software converts the cloud index to the surface solar irradiance using the Heliosat method (Mueller et al. 2009). The MAGIC algorithm is also used by the CM-SAF surface solar irradiance product for clear sky cases. We applied the MAGIC software to FRESCO effective cloud fraction with slight modifications. In this presentation we will show the FRESCO-SSI monthly mean product and the comparison with the BSRN global irradiance data at Cabauw, the Netherlands and surface solar irradiance measurement at Tibetan plateau in China.

  3. Adhesion of adipose-derived mesenchymal stem cells to glycosaminoglycan surfaces with different protein patterns.

    PubMed

    Soares da Costa, Diana; Márquez-Posadas, Maria del Carmen; Araujo, Ana R; Yang, Yuan; Merino, Santos; Groth, Thomas; Reis, Rui L; Pashkuleva, Iva

    2015-05-13

    Proteins and glycosaminoglycans (GAGs) are the main constituents of the extracellular matrix (ECM). They act in synergism and are equally critical for the development, growth, function, or survival of an organism. In this work, we developed surfaces that display these two classes of biomacromolecules, namely, GAGs and proteins, in a spatially controlled fashion. The generated surfaces can be used as a minimalistic but straightforward model aiding the elucidation of cell-ECM interactions. GAGs (hyaluronic acid and heparin) were covalently bound to amino functionalized surfaces, and albumin or fibronectin was patterned by microcontact printing on top of them. We demonstrate that adipose-derived stem cells (ASCs) can adhere either on the protein or on the GAG pattern as a function of the patterned molecules. ASCs found on the GAG pattern had different morphology and expressed different surface markers than the cells adhered on the protein pattern. ASCs morphology and spreading were also dependent on the size of the pattern. These results show that the developed supports can also be used for ASCs differentiation into different lineages.

  4. Boundary layer drag reduction research hypotheses derived from bio-inspired surface and recent advanced applications.

    PubMed

    Luo, Yuehao; Yuan, Lu; Li, Jianhua; Wang, Jianshe

    2015-12-01

    Nature has supplied the inexhaustible resources for mankind, and at the same time, it has also progressively developed into the school for scientists and engineers. Through more than four billions years of rigorous and stringent evolution, different creatures in nature gradually exhibit their own special and fascinating biological functional surfaces. For example, sharkskin has the potential drag-reducing effect in turbulence, lotus leaf possesses the self-cleaning and anti-foiling function, gecko feet have the controllable super-adhesion surfaces, the flexible skin of dolphin can accelerate its swimming velocity. Great profits of applying biological functional surfaces in daily life, industry, transportation and agriculture have been achieved so far, and much attention from all over the world has been attracted and focused on this field. In this overview, the bio-inspired drag-reducing mechanism derived from sharkskin is explained and explored comprehensively from different aspects, and then the main applications in different fluid engineering are demonstrated in brief. This overview will inevitably improve the comprehension of the drag reduction mechanism of sharkskin surface and better understand the recent applications in fluid engineering. PMID:26348428

  5. Boundary layer drag reduction research hypotheses derived from bio-inspired surface and recent advanced applications.

    PubMed

    Luo, Yuehao; Yuan, Lu; Li, Jianhua; Wang, Jianshe

    2015-12-01

    Nature has supplied the inexhaustible resources for mankind, and at the same time, it has also progressively developed into the school for scientists and engineers. Through more than four billions years of rigorous and stringent evolution, different creatures in nature gradually exhibit their own special and fascinating biological functional surfaces. For example, sharkskin has the potential drag-reducing effect in turbulence, lotus leaf possesses the self-cleaning and anti-foiling function, gecko feet have the controllable super-adhesion surfaces, the flexible skin of dolphin can accelerate its swimming velocity. Great profits of applying biological functional surfaces in daily life, industry, transportation and agriculture have been achieved so far, and much attention from all over the world has been attracted and focused on this field. In this overview, the bio-inspired drag-reducing mechanism derived from sharkskin is explained and explored comprehensively from different aspects, and then the main applications in different fluid engineering are demonstrated in brief. This overview will inevitably improve the comprehension of the drag reduction mechanism of sharkskin surface and better understand the recent applications in fluid engineering.

  6. Superhydrophobic films on glass surface derived from trimethylsilanized silica gel nanoparticles.

    PubMed

    Goswami, Debmita; Medda, Samar Kumar; De, Goutam

    2011-09-01

    The paper deals with the fabrication of sol-gel-derived superhydrophobic films on glass based on the macroscopic silica network with surface modification. The fabricated transparent films were composed of a hybrid -Si(CH(3))(3)-functionalized SiO(2) nanospheres exhibiting the desired micro/nanostructure, water repellency, and antireflection (AR) property. The wavelength selective AR property can be tuned by controlling the physical thickness of the films. Small-angle X-ray scattering (SAXS) studies revealed the existence of SiO(2) nanoparticles of average size ∼9.4 nm in the sols. TEM studies showed presence of interconnected SiO(2) NPs of ∼10 nm in size. The films were formed with uniformly packed SiO(2) aggregates as observed by FESEM of film surface. FTIR of the films confirmed presence of glasslike Si-O-Si bonding and methyl functionalization. The hydrophobicity of the surface was depended on the thickness of the deposited films. A critical film thickness (>115 nm) was necessary to obtain the air push effect for superhydrophobicity. Trimethylsilyl functionalization of SiO(2) and the surface roughness (rms ≈30 nm as observed by AFM) of the films were also contributed toward the high water contact angle (WCA). The coated glass surface showed WCA value of the droplet as high as 168 ± 3° with 6 μL of water. These superhydrophobic films were found to be stable up to about 230-240 °C as confirmed by TG/DTA studies, and WCA measurements of the films with respect to the heat-treatment temperatures. These high water repellant films can be deposited on relatively large glass surfaces to remove water droplets immediately without any mechanical assistance. PMID:21823656

  7. Superhydrophobic films on glass surface derived from trimethylsilanized silica gel nanoparticles.

    PubMed

    Goswami, Debmita; Medda, Samar Kumar; De, Goutam

    2011-09-01

    The paper deals with the fabrication of sol-gel-derived superhydrophobic films on glass based on the macroscopic silica network with surface modification. The fabricated transparent films were composed of a hybrid -Si(CH(3))(3)-functionalized SiO(2) nanospheres exhibiting the desired micro/nanostructure, water repellency, and antireflection (AR) property. The wavelength selective AR property can be tuned by controlling the physical thickness of the films. Small-angle X-ray scattering (SAXS) studies revealed the existence of SiO(2) nanoparticles of average size ∼9.4 nm in the sols. TEM studies showed presence of interconnected SiO(2) NPs of ∼10 nm in size. The films were formed with uniformly packed SiO(2) aggregates as observed by FESEM of film surface. FTIR of the films confirmed presence of glasslike Si-O-Si bonding and methyl functionalization. The hydrophobicity of the surface was depended on the thickness of the deposited films. A critical film thickness (>115 nm) was necessary to obtain the air push effect for superhydrophobicity. Trimethylsilyl functionalization of SiO(2) and the surface roughness (rms ≈30 nm as observed by AFM) of the films were also contributed toward the high water contact angle (WCA). The coated glass surface showed WCA value of the droplet as high as 168 ± 3° with 6 μL of water. These superhydrophobic films were found to be stable up to about 230-240 °C as confirmed by TG/DTA studies, and WCA measurements of the films with respect to the heat-treatment temperatures. These high water repellant films can be deposited on relatively large glass surfaces to remove water droplets immediately without any mechanical assistance.

  8. Synthesis and self-assembly of thio derivatives of calix[4]arene on noble metal surfaces.

    PubMed

    Genorio, Bostjan; He, Tao; Meden, Anton; Polanc, Slovenko; Jamnik, Janko; Tour, James M

    2008-10-21

    Self-assembled monolayers (SAMs) provide a simple route to functionalize electrode surfaces with organic molecules. Herein we use cavity-containing derivatives of calix[4]arenes in SAMs. Bound to noble metal surface, the assembled molecules are candidates to serve as molecular sieves for H 2 molecules and H (+) ions, which could have relevance for fuel cell applications. Tetra- O-alkylated calix[4]arenes with thiolacetate and thiolamide wide-rim anchoring groups in cone and partial-cone conformations were designed, synthesized and self-assembled onto Au, Pt, and Pd surfaces. The resulting SAMs were systematically examined. Single crystal X-ray diffraction of 5,11,17,23-tetrakis(thioacetyl)-25,26,27,28-tetra- i-propoxycalix[4]arene confirmed the cone conformation and revealed the cavity dimensions of the SAMs that were formed by immersing noble metal substrates (Au, Pt and Pd deposited on Si-wafers) in solutions of calix[4]arenes. Surface characterization techniques including ellipsometry, cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS) were used, indicating that the metal surface is terminated with a monomolecular layer. Experimental thicknesses obtained from the ellipsometry are consistent with the calculated values. CV results showed 50 to 80% physical passivation against the Fe(CN) 6 (3-/4-) couple, implying an overall relatively low concentration of defects and pinholes in the films. The binding energies of the S2p core level in the XPS were consistent with the literature values and revealed that up to 3.2 out of four anchoring groups were bonded to the noble metal surface.

  9. Surface Irradiances Consistent With CERES-Derived Top-of-Atmosphere Shortwave and Longwave Irradiances

    NASA Technical Reports Server (NTRS)

    Kato, Seiji; Loeb, Norman G.; Rose, Fred G.; Doelling, David R.; Rutan, David A.; Caldwell, Thomas E.; Yu, Lisan; Weller, Robert A.

    2013-01-01

    The estimate of surface irradiance on a global scale is possible through radiative transfer calculations using satellite-retrieved surface, cloud, and aerosol properties as input. Computed top-of-atmosphere (TOA) irradiances, however, do not necessarily agree with observation-based values, for example, from the Clouds and the Earth's Radiant Energy System (CERES). This paper presents amethod to determine surface irradiances using observational constraints of TOA irradiance from CERES. A Lagrange multiplier procedure is used to objectively adjust inputs based on their uncertainties such that the computed TOA irradiance is consistent with CERES-derived irradiance to within the uncertainty. These input adjustments are then used to determine surface irradiance adjustments. Observations by the Atmospheric Infrared Sounder (AIRS), Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO), CloudSat, andModerate Resolution Imaging Spectroradiometer (MODIS) that are a part of the NASA A-Train constellation provide the uncertainty estimates. A comparison with surface observations from a number of sites shows that the bias [root-mean-square (RMS) difference] between computed and observed monthlymean irradiances calculated with 10 years of data is 4.7 (13.3) W/sq m for downward shortwave and 22.5 (7.1) W/sq m for downward longwave irradiances over ocean and 21.7 (7.8) W m22 for downward shortwave and 21.0 (7.6) W/sq m for downward longwave irradiances over land. The bias andRMS error for the downward longwave and shortwave irradiances over ocean are decreased from those without constraint. Similarly, the bias and RMS error for downward longwave over land improves, although the constraint does not improve downward shortwave over land. This study demonstrates how synergetic use of multiple instruments (CERES,MODIS, CALIPSO, CloudSat, AIRS, and geostationary satellites) improves the accuracy of surface irradiance computations.

  10. 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.

  11. 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.

  12. Development of New Electrochemical Synthesis of Oxides: Electrolytic Deposition of La2CuO4 Thick Layer on Zirconia Surface in Molten Salt

    NASA Astrophysics Data System (ADS)

    Nakamura, Tetsurō; Natsuhara, Masuhiro; Kawaji, Hitoshi; Itoh, Mitsuru

    1991-08-01

    A new method for electrochemical synthesis of oxides in molten salt was developed. The following galvanic cell was assembled and electrolysis was carried out at 973 K between the electrodes LaB6 vs Pt/O2 and between Cu vs Pt/O2 simultaneously. Pt, LaB6 |80%KCl-14%NaCl-(6-x)%LaCl3-x%CuCl2|ZrO2(Y2O3)|O2, Pt Pt, Cu Formation of almost-single-phased La2CuO4 on the ZrO2(Y2O3) surface was confirmed when the ratio of electric currents passed through electrodes LaB6 vs Pt/O2 and Cu vs Pt/O2 was controlled to 3:1.1 and the molten salt composition was fixed at 80%KCl-14%NaCl-6%LaCl3.

  13. Toward Improved Solar Irradiance Forecasts: Derivation of Downwelling Surface Shortwave Radiation in Arizona from Satellite

    NASA Astrophysics Data System (ADS)

    Kim, Chang Ki; Holmgren, William F.; Stovern, Michael; Betterton, Eric A.

    2016-07-01

    Over the past few decades, substantial progress has been made in the retrieval of surface shortwave radiation from satellite measurements for the Earth's energy budget as well as solar energy applications. We present a new algorithm to derive the downwelling surface shortwave radiation for the Southwestern US using geostationary satellite products. A look-up table generated by the Goddard Space Flight Center Radiative Transfer Model is employed to derive the shortwave radiation at the ground by comparing observed and modeled top of atmosphere shortwave albedo. The algorithm was compared to ground observation stations at three locations, such as the University of Arizona, the University of Nevada, Las Vegas, and Desert Rock, NV. For all sky conditions, the average values of root-mean-square error between the instantaneous estimates and in situ measurements ranged from 84.2 to 89.4 W m-2 and were 30 W m-2 when evaluated on daily time scales. The error statistics were considerably better for clear sky than for cloudy sky. The average values of instantaneous root-mean-square error for the clear-sky conditions range from 39.4 to 43.7 W m-2, while average root-mean-square error for the cloudy-sky conditions is between 137.0 and 141.2 W m-2.

  14. Data Assimilation of Satellite-Derived Surface Water Extent into a Global Rainfall-Runoff Model

    NASA Astrophysics Data System (ADS)

    Wanders, N.; Revilla-Romero, B.; Burek, P.; Salamon, P.; De Roo, A. P. J.

    2015-12-01

    In hydrological forecasting, data assimilation techniques are employed to improve estimates of initial conditions to update incorrect model states with observational data. However, the limited availability of continuous and up-to-date ground observational data is one of the main challenges for real-time applications such as global flood forecasting models. Remote sensing has been recognised as a valuable alternative source of observations of land surface hydrological fluxes and state variables due to its global coverage, open data policy and the advantage of being available at frequent temporal intervals and shortly after the satellite image retrieval. In this study, we present the impact of assimilating remotely sensed surface water extent into the global hydrological LISFLOOD model using Ensemble Kalman Filter (EnFK) and its potential to improve the timing of the flood peak. We use the merged product from Global Flood Detection System (GFDS) that employs both AMSR-E (Advance Microwave Scanning Radiometer - Earth Observing System) and TRMM (Tropical Rainfall Measuring Mission) to derive water extent as used in the GFDS. This satellite-derived water extent signal is assimilated into LISFLOOD for selected catchments and results are compared to baseline initial conditions (without data assimilation). Validation is done based on ground-based discharge observations. Furthermore, we discuss the post-processing and data assimilation strategies of satellite data within a global hydrological model.

  15. Advection of surface-derived organic carbon fuels microbial reduction in Bangladesh groundwater

    NASA Astrophysics Data System (ADS)

    Mailloux, Brian J.; Trembath-Reichert, Elizabeth; Cheung, Jennifer; Watson, Marlena; Stute, Martin; Freyer, Greg A.; Ferguson, Andrew S.; Matin Ahmed, Kazi; Jahangir Alam, Md.; Buchholz, Bruce A.; Thomas, James; Layton, Alice C.; Zheng, Yan; Bostick, Benjamin C.; van Geen, Alexander

    2013-04-01

    Chronic exposure to arsenic (As) by drinking shallow groundwater causes widespread disease in Bangladesh and neighboring countries. The release of As naturally present in sediment to groundwater has been linked to the reductive dissolution of iron oxides coupled to the microbial respiration of organic carbon (OC). The source of OC driving this microbial reduction-carbon deposited with the sediments or exogenous carbon transported by groundwater-is still debated despite its importance in regulating aquifer redox status and groundwater As levels. Here, we used the radiocarbon (14C) signature of microbial DNA isolated from groundwater samples to determine the relative importance of surface and sediment-derived OC. Three DNA samples collected from the shallow, high-As aquifer and one sample from the underlying, low-As aquifer were consistently younger than the total sediment carbon, by as much as several thousand years. This difference and the dominance of heterotrophic microorganisms implies that younger, surface-derived OC is advected within the aquifer, albeit more slowly than groundwater, and represents a critical pool of OC for aquifer microbial communities. The vertical profile shows that downward transport of dissolved OC is occurring on anthropogenic timescales, but bomb 14C-labeled dissolved OC has not yet accumulated in DNA and is not fueling reduction. These results indicate that advected OC controls aquifer redox status and confirm that As release is a natural process that predates human perturbations to groundwater flow. Anthropogenic perturbations, however, could affect groundwater redox conditions and As levels in the future.

  16. Comparison of AMSR-E derived Antarctic snow-ice interface temperatures with previous surface observations

    NASA Astrophysics Data System (ADS)

    Lewis, M.; Ackley, S. F.; Xie, H.; Cicek, B.

    2006-12-01

    The AMSR-E Sea Ice Temperature (L3 25 km) data product derived from passive microwave emissions at 6.9 GHz is available from the National Snow and Ice Data Center. The Sea Ice Temperature data represents the temperature at the surface of the sea ice, or the temperature corresponding to the snow-ice interface. Antarctic sea ice images from 2005 were obtained at approximate 5-day intervals corresponding to typical days of the four seasons, winter, spring, summer and fall. Available measurements conducted during previous field campaigns were obtained from the literature. The field data of snow-ice interface temperatures roughly corresponding to the typical days of the four seasons, albeit over much more limited areas of ice cover and at times different from the satellite images, were utilized for comparison. The field measurements give insight into the physical behavior of the Antarctic ice surface temperature. These field data show: 1) during the summer season, mean ice surface temperatures invariably range from 0 to -2ºC, corresponding to an isothermal snowpack or surface flooded with ocean water; 2) during the spring season, mean ice surface temperatures are generally above -8ºC, as increases in air temperature and solar radiation result in interface temperatures that lie between the air temperature (mean above -10ºC) and the seawater temperature at the ice-water interface (-1.8ºC); 3) during fall and winter seasons, warmest interface temperatures are found beneath the deepest snow cover, which either better insulates the surface from colder air temperatures than thin snow cover or causes surface flooding from the increased overburden, leading to sea ice interface temperatures near -1.8ºC. While the field data are not a validation sensu strictu, the AMSR-E product appears to conflict with several of these generally observed properties. The coldest interface temperatures from the satellite data are reported for spring and summer, which are lower than winter

  17. 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

  18. Potential of Multitemporal Tandem-X Derived Crop Surface Models for Maize Growth Monitoring

    NASA Astrophysics Data System (ADS)

    Hütt, C.; Tilly, N.; Schiedung, H.; Bareth, G.

    2016-06-01

    In this study, first results of retrieving plant heights of maize fields from multitemporal TanDEM-X images are shown. Three TanDEM-X dual polarization spotlight acquisitions were taken over a rural area in Germany in the growing season 2014. By interferometric processing, digital terrain models (DTM) were derived for each date with 5m resolution. From the data of the first acquisition (June 1st) taken before planting, a DTM of the bare ground is generated. The data of the following acquisition dates (July 15th, July 26th) are used to establish crop surface models (CSM). A CSM represents the crop surface of a whole field in a high resolution. By subtracting the DTM of the ground from each CSM, the actual plant height is calculated. Within these data sets 30 maize fields in the area of interest could be detected and verified by external land use data. Besides the spaceborne measurements, one of the maize fields was intensively investigated using terrestrial laser scanning (TLS), which was carried out at the same dates as the predicted TanDEM-X acquisitions. Visual inspection of the derived plant heights, and accordance of the individually processed polarisations over the maize fields, demonstrate the feasibility of the proposed method. Unfortunately, the infield variability of the intensively monitored field could not be successfully captured in the TanDEM-X derived plant heights and merely the general trend is visible. Nevertheless, the study shows the potential of the TanDEM-X constellation for maize height monitoring on field level.

  19. Electrochemical epoxidation of olefins

    SciTech Connect

    van der Eijk, J.M. )

    1987-08-01

    Direct epoxidation of an olefin, using oxygen and a catalyst, only proceeds with a high yield in the case of ethene. All commercial processes for the epoxidation of higher olefins therefore make use of an indirect route, yielding a co-product besides the desired epoxide. From an economic point of view this is an unfavorable situation since it couples the manufacture of two products. Recently, we have made a comprehensive study of a non-conventional method involving the electrochemical oxidation of olefins to epoxides. The major technical challenge posed by the electrochemical route to epoxides is the identification of conditions under which the desired reaction proceeds selectively. An exploratory study had indicated that the direct oxidation of olefins at the surface of catalytically active anodes (Pt, silver oxide, nickel oxide, lead ruthenates (1)) proceeds either slowly or non-selectively. A more promising approach was expected to be electrochemical (re)generation of an epoxidation agent at the anode of an electrochemical cell and carrying out the epoxidation in the anolyte solution. Epoxidation agents of interest included thallium (III) acetate complexes, hypobromite and silver(II)-pyridine complexes. Here we report on the electrochemical oxidation of olefins as mediated by silver-pyridine complexes. Subjects to be dealt with include the chemical efficacy of the process as well as the kinettics and mechanism of the olefin-Ag(II) reaction.

  20. 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.