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Sample records for applied electrochemistry prikladnaya

  1. Investigation of the Interface between Two Immiscible Electrolytes Applied to Membrane Electrochemistry

    DTIC Science & Technology

    1988-10-13

    microinterface. PUBLICATIONS D. H. Wiegand and P. Van~sek: Spectroscopic and fluorometric characterization of oxacyanine dyes in water and nitrobenzene. Applied ... Spectroscopy , 42, 958, (1988) D. H. Wiegand and P. Vansek: Potentiometric studies of oxacyanine dyes on L/L interfaces, J. Electroanal. Chem., Submitted

  2. FUNDAMENTAL STUDIES IN ELECTROCHEMISTRY.

    DTIC Science & Technology

    ORGANIC PHOSPHORUS COMPOUNDS), (*ELECTROCHEMISTRY, OXIDATION, REDUCTION, SULFIDES, PHOSPHINE OXIDES, CATALYSTS , FLUORINE COMPOUNDS, BENZENE, POLAROGRAPHIC ANALYSIS, ADSORPTION, ELECTROLYSIS, ELECTRODES.

  3. DNA-Mediated Electrochemistry

    PubMed Central

    Gorodetsky, Alon A.; Buzzeo, Marisa C.

    2009-01-01

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

  4. Electrochemistry in supercritical fluids

    PubMed Central

    Branch, Jack A.; Bartlett, Philip N.

    2015-01-01

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

  5. Electrochemistry in supercritical fluids.

    PubMed

    Branch, Jack A; Bartlett, Philip N

    2015-12-28

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

  6. Students' understandings of electrochemistry

    NASA Astrophysics Data System (ADS)

    O'Grady-Morris, Kathryn

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

  7. Dynamic Electrochemistry: Methodology and Applications.

    ERIC Educational Resources Information Center

    Johnson, Dennis C.; And Others

    1984-01-01

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

  8. Physical electrochemistry of nanostructured devices.

    PubMed

    Bisquert, Juan

    2008-01-07

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

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

    ERIC Educational Resources Information Center

    Kissinger, Peter T.

    1983-01-01

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

  10. Fundamentals and applications of electrochemistry

    NASA Astrophysics Data System (ADS)

    McEvoy, A. J.

    2013-06-01

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

  11. Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

    SciTech Connect

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

    2016-05-04

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

  12. Factors that Prevent Learning in Electrochemistry

    ERIC Educational Resources Information Center

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

    2007-01-01

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

  13. Modern aspects of electrochemistry

    SciTech Connect

    White, R.E.; Bockris, J.O'M.; Conway, B.E.

    1983-01-01

    This book focuses on topics at the forefront of electrochemical research. Splitting water by electrolysis; splitting water by visible light; the recent development of lithium batteries; theoretical approaches to intercalation; and fundamental concepts of electrode kinetics, particularly as applied to semiconductors are discussed. It is recommended for electrochemists, physical chemists, corrosion scientists, and those working in the fields of analytical chemistry, surface and colloid science, materials science, electrical engineering, and chemical engineering.

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

    PubMed

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

    2014-01-01

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

  15. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.

    1992-05-01

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

  16. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-02-01

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

  17. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1992-01-01

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

  18. Graphene-based nanomaterials and their electrochemistry.

    PubMed

    Pumera, Martin

    2010-11-01

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

  19. Electrochemistry in the General Chemistry Curriculum.

    ERIC Educational Resources Information Center

    Chambers, James Q.

    1983-01-01

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

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

    ERIC Educational Resources Information Center

    Rodriguez-Velazquez, Sorangel

    2013-01-01

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

  1. Electrochemistry at carbon nanotubes: perspective and issues.

    PubMed

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

    2009-12-07

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

  2. NASA Glenn Research Center Electrochemistry Branch Overview

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

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

  3. Electrochemistry of Main-Group Phthalocyanines.

    DTIC Science & Technology

    1981-07-30

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

  4. The merger of electrochemistry and molecular electronics.

    PubMed

    McCreery, Richard L

    2012-02-01

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

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

    ERIC Educational Resources Information Center

    Johnson, Dennis C.

    1980-01-01

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

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

    ERIC Educational Resources Information Center

    Heineman, William R.; Kissinger, Peter T.

    1980-01-01

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

  7. Graphene and its electrochemistry - an update.

    PubMed

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

    2016-05-07

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

  8. Molybdenum, molybdenum oxides, and their electrochemistry.

    PubMed

    Saji, Viswanathan S; Lee, Chi-Woo

    2012-07-01

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

  9. Organic Electrochemistry in Aluminum Chloride Melts.

    DTIC Science & Technology

    1976-08-15

    CLASS. (.5 Uit• “P.’U (21F,n~!ye~ t . _ _ _ _ _ _ _ _ _ _ _ _I .~~. cY~ t 7~ .3~ ~‘l+g 7~ \\ ii.. kt~~I1ICAY* ONYCO ~ $GRA D*$G IU OIITRIIUTIOM STATEMENT (.1...DOCUMENTATION PAGE 8aFO CO~~~~~~~ NC~ PORM i. REPORT NUNSER 3. GOVT ACCIIZION NO 3. RtC,PIENt ’i C A T A ~ O~~ NUN.LR TIY ~.E (~~~~3~.AtIaS.) I YVPE OF...REPORT I PERIOD COVERED Final- 1 October 1972- • t ~~ ‘~~~~ _ ( Organic Electrochemistry in Al uminum .-~~ 30 May 1976 ~ L ~~~~~~~~~~~~~~~ I •. •i~ ,o

  10. Electrochemistry-based Battery Modeling for Prognostics

    NASA Technical Reports Server (NTRS)

    Daigle, Matthew J.; Kulkarni, Chetan Shrikant

    2013-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Nazri, Maryam

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  13. Perspective on Electrospray Ionization and Its Relation to Electrochemistry

    NASA Astrophysics Data System (ADS)

    Pozniak, Boguslaw P.; Cole, Richard B.

    2015-03-01

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

  14. The Mesoscopic Electrochemistry of Molecular Junctions

    PubMed Central

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

    2016-01-01

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

  15. DNA Electrochemistry with Tethered Methylene Blue

    PubMed Central

    Pheeney, Catrina G.

    2012-01-01

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

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

    PubMed

    Loget, Gabriel; Kuhn, Alexander

    2011-06-01

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

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

    PubMed

    Gao, Lixia; Teng, Yong

    2016-04-01

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

  18. Workshop on the frontiers of theoretical and experimental electrochemistry

    SciTech Connect

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

    1986-01-01

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

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

    SciTech Connect

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

    2015-01-07

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

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

    PubMed

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

    2015-08-07

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

  1. Chelating ionic liquids for reversible zinc electrochemistry.

    PubMed

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

    2013-05-21

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

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

    PubMed

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

    2016-09-20

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

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

    ERIC Educational Resources Information Center

    Karamustafaoglu, Sevilay; Mamlok-Naaman, Rachel

    2015-01-01

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

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

    ERIC Educational Resources Information Center

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

    2000-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Michael, Adrian C.

    2007-04-01

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

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

    ERIC Educational Resources Information Center

    Sanger, Michael J.; Greenbowe, Thomas J.

    1997-01-01

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

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

    SciTech Connect

    Liu, S.H.

    1990-09-24

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

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

    ERIC Educational Resources Information Center

    Moran, P. J.; Gileadi, E.

    1989-01-01

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

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

    PubMed

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    PubMed

    Dohm, Sebastian; Spohr, Eckhard; Korth, Martin

    2017-01-05

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2013-12-09

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

  16. Coupling Electrochemistry with Probe Electrospray Ionization Mass Spectrometry.

    PubMed

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

    2016-04-18

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

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

    PubMed

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

    2016-03-24

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

  18. 2010 ELECTROCHEMISTRY GRC, JANUARY 9-15, 2010, VENTURA, CA

    SciTech Connect

    Stephen Creager

    2010-12-31

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

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

    NASA Astrophysics Data System (ADS)

    Rodriguez-Velazquez, Sorangel

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

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

    PubMed

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

    2011-05-19

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

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

    PubMed

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

    2014-01-07

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

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

    PubMed

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

    2016-11-15

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

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

    ERIC Educational Resources Information Center

    Niaz, Mansoor; Chacon, Eleazar

    2003-01-01

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

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

    PubMed

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

    2012-11-07

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

  5. Electrospray ion source with reduced analyte electrochemistry

    DOEpatents

    Kertesz, Vilmos [Knoxville, TN; Van Berkel, Gary [Clinton, TN

    2011-08-23

    An electrospray ion (ESI) source and method capable of ionizing an analyte molecule without oxidizing or reducing the analyte of interest. The ESI source can include an emitter having a liquid conduit, a working electrode having a liquid contacting surface, a spray tip, a secondary working electrode, and a charge storage coating covering partially or fully the liquid contacting surface of the working electrode. The liquid conduit, the working electrode and the secondary working electrode can be in liquid communication. The electrospray ion source can also include a counter electrode proximate to, but separated from, said spray tip. The electrospray ion source can also include a power system for applying a voltage difference between the working electrodes and a counter-electrode. The power system can deliver pulsed voltage changes to the working electrodes during operation of said electrospray ion source to minimize the surface potential of the charge storage coating.

  6. Construction and direct electrochemistry of orientation controlled laccase electrode

    SciTech Connect

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

    2014-03-28

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

  7. Facile synthesis of cuprous oxide nanoparticles by plasma electrochemistry

    NASA Astrophysics Data System (ADS)

    Chen, Qiang; Liu, Jiandi; Yue, Guanghui

    2015-09-01

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

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

    PubMed

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

    2013-11-19

    Bipolar electrochemistry, a phenomenon which generates an asymmetric reactivity on the surface of conductive objects in a wireless manner, is an important concept for many purposes, from analysis to materials science as well as for the generation of motion. Chemists have known the basic concept for a long time, but it has recently attracted additional attention, especially in the context of micro- and nanoscience. In this Account, we introduce the fundamentals of bipolar electrochemistry and illustrate its recent applications, with a particular focus on the fields of materials science and dynamic systems. Janus particles, named after the Roman god depicted with two faces, are currently in the heart of many original investigations. These objects exhibit different physicochemical properties on two opposite sides. This makes them a unique class of materials, showing interesting features. They have received increasing attention from the materials science community, since they can be used for a large variety of applications, ranging from sensing to photosplitting of water. So far the great majority of methods developed for the generation of Janus particles breaks the symmetry by using interfaces or surfaces. The consequence is often a low time-space yield, which limits their large scale production. In this context, chemists have successfully used bipolar electrodeposition to break the symmetry. This provides a single-step technique for the bulk production of Janus particles with a high control over the deposit structure and morphology, as well as a significantly improved yield. In this context, researchers have used the bipolar electrodeposition of molecular layers, metals, semiconductors, and insulators at one or both reactive poles of bipolar electrodes to generate a wide range of Janus particles with different size, composition and shape. In using bipolar electrochemistry as a driving force for generating motion, its intrinsic asymmetric reactivity is again the

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

    DOE PAGES

    Yang, Sangmo; Strelcov, Evgheni; Paranthaman, Mariappan Parans; ...

    2015-01-07

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

  10. Electroanalytical Evaluation of Nanoparticles by Nano-impact Electrochemistry

    NASA Astrophysics Data System (ADS)

    Karimi, Anahita

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

  11. Electrochemistry-mass spectrometry for mechanistic studies and simulation of oxidation processes in the environment.

    PubMed

    Hoffmann, Th; Hofmann, D; Klumpp, E; Küppers, S

    2011-02-01

    Electrochemistry (EC) coupled to mass spectrometry (MS) has already been successfully applied to metabolism research for pharmaceutical applications, especially for the oxidation behaviour of drug substances. Xenobiotics (chemicals in the environment) also undergo various conversions; some of which are oxidative reactions. Therefore, EC-MS might be a suitable tool for the investigation of oxidative behaviour of xenobiotics. A further evaluation of this approach to environmental research is presented in the present paper using sulfonamide antibiotics. The results with sulfadiazine showed that EC-MS is a powerful tool for the elucidation of the oxidative degradation mechanism within a short time period. In addition, it was demonstrated that EC-MS can be used as a fast and easy method to model the chemical binding of xenobiotics to soil. The reaction of sulfadiazine with catechol, as a model substance for organic matter in soil, led to the expected chemical structure. Finally, by using EC-MS a first indication was obtained of the persistence of a component under chemical oxidation conditions for the comparison of the oxidative stability of different classes of xenobiotics. Overall, using just a few examples, the study demonstrates that EC-MS can be applied as a versatile tool for mechanistic studies of oxidative degradation pathways of xenobiotics and their possible interaction with soil organic matter as well as their oxidative stability in the environment. Further studies are needed to evaluate the full range of possibilities of the application of EC-MS in environmental research.

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

    DOE PAGES

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

    2016-04-21

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

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

    PubMed

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

    2013-04-16

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

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

    PubMed

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

    2014-01-03

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

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

    NASA Astrophysics Data System (ADS)

    Lehmann, Volker

    2002-04-01

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

  16. Facile synthesis of cuprous oxide nanoparticles by plasma electrochemistry

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    SciTech Connect

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

    2005-05-15

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

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

    PubMed

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

    2013-09-24

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

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

    PubMed

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

    2006-02-01

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

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

    PubMed

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

    2008-01-01

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

  1. Using the Electrochemistry of the Electrospray Ion Source

    SciTech Connect

    Van Berkel, Gary J; Kertesz, Vilmos

    2007-01-01

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

  2. Electrochemistry combined on-line with electrospray mass spectrometry

    SciTech Connect

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

    1995-10-15

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

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

    SciTech Connect

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

    2005-06-01

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

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

    PubMed

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

    1996-09-11

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

  5. Martian dust devil electron avalanche process and associated electrochemistry

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

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

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

    NASA Astrophysics Data System (ADS)

    Llano, Jorge; Eriksson, Leif A.

    2002-12-01

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

  7. Martian Dust Devil Electron Avalanche Process and Associated Electrochemistry

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

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

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

    PubMed

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

    2006-08-01

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

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

    SciTech Connect

    Keller, David W.

    2005-01-01

    Electrochemically modulated liquid chromatography (EMLC) employs a conductive material as both a stationary phase for chromatographic separations and as a working electrode for performing electrochemistry experiments. This dual functionality gives EMLC the capacity to manipulate chromatographic separations by changing the potential applied (Eapp) to the stationary phase with respect to an external reference. The ability to monitor retention as a function of Eapp provides a means to chromatographically monitor electrosorption processes at solid-liquid interfaces. In this dissertation, the retention mechanism for EMLC is examined from the perspective of electrical double layer theory and interfacial thermodynamics. From the chromatographic data, it is possible to determine the interfacial excess (Λ) of a solute and changes in interfacial tension (dγ) as a function of both Eapp and the supporting electrolyte concentration. Taken together, these two experimentally manipulated parameters can be examined within the context of the Gibbs adsorption equation to delineate the contribution of a variety of interfacial properties, including the charge of solute on the stationary phase and the potential of zero charge (PZC), to the mechanism behind EMLC-based retention. The chromatographic probing of interfacial phenomena is complemented by electroanalytical experiments that exploit the ability to monitor the electronic current flowing through an EMLC column. Cyclic voltammetry and chronoamperometry of an EMLC column are used to determine the electronic performance characteristics of an EMLC column. An electrochemical flow injection analysis of a column is provided in which the current required to maintain a constant Eapp is monitored and provides a way to examine the influence that acetonitrile and supporting electrolyte composition, flow rate, column backpressure, and ionic strength have on the structure of electrified interfaces.

  10. Serendipity: Genesis of the Electrochemical Instrumentation at Princeton Applied Research Corporation

    ERIC Educational Resources Information Center

    Flato, J. B.

    2007-01-01

    Princeton Applied Research Corporation (PAR) was a small electronic instrument company in early 1960s but once they entered electrochemistry they were very successful. Since then they have developed and designed successful instruments with their tremendous knowledge and have made great contribution to the field of analytical chemistry.

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

    ERIC Educational Resources Information Center

    Sesen, Burcin Acar; Tarhan, Leman

    2013-01-01

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

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

    ERIC Educational Resources Information Center

    Garnett, Pamela J.; Treagust, David F.

    1992-01-01

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

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

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1996-01-01

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

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

    ERIC Educational Resources Information Center

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

    2004-01-01

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

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

    ERIC Educational Resources Information Center

    Doymus, Kemal; Karacop, Ataman; Simsek, Umit

    2010-01-01

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

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

    ERIC Educational Resources Information Center

    Günter, Tugçe; Alpat, Sibel Kilinç

    2017-01-01

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

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

    PubMed

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

    2015-11-02

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

  18. Bipolar Electrochemistry for Concurrently Evaluating the Stability of Anode and Cathode Electrocatalysts and the Overall Cell Performance during Long-Term Water Electrolysis.

    PubMed

    Eßmann, Vera; Barwe, Stefan; Masa, Justus; Schuhmann, Wolfgang

    2016-09-06

    Electrochemical efficiency and stability are among the most important characteristics of electrocatalysts. These parameters are usually evaluated separately for the anodic and cathodic half-cell reactions in a three-electrode system or by measuring the overall cell voltage between the anode and cathode as a function of current or time. Here, we demonstrate how bipolar electrochemistry can be exploited to evaluate the efficiency of electrocatalysts for full electrochemical water splitting while simultaneously and independently monitoring the individual performance and stability of the half-cell electrocatalysts. Using a closed bipolar electrochemistry setup, all important parameters such as overvoltage, half-cell potential, and catalyst stability can be derived from a single galvanostatic experiment. In the proposed experiment, none of the half-reactions is limiting on the other, making it possible to precisely monitor the contribution of the individual half-cell reactions on the durability of the cell performance. The proposed approach was successfully employed to investigate the long-term performance of a bifunctional water splitting catalyst, specifically amorphous cobalt boride (Co2B), and the durability of the electrocatalyst at the anode and cathode during water electrolysis. Additionally, by periodically alternating the polarization applied to the bipolar electrode (BE) modified with a bifunctional oxygen electrocatalyst, it was possible to explicitly follow the contributions of the oxygen reduction (ORR) and the oxygen evolution (OER) half-reactions on the overall long-term durability of the bifunctional OER/ORR electrocatalyst.

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

    NASA Astrophysics Data System (ADS)

    Hastings, Jason Thomas

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

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

    SciTech Connect

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

    2011-10-13

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

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

    SciTech Connect

    Kinoshita, K.; Scherson, D.

    1998-02-01

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

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

    SciTech Connect

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

    2011-12-01

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

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

    PubMed

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

    2011-05-01

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

  4. Analysis of cysteine-containing proteins using precolumn derivatization with N-(2-ferroceneethyl)maleimide and liquid chromatography/electrochemistry/mass spectrometry.

    PubMed

    Seiwert, Bettina; Karst, Uwe

    2007-08-01

    N-(2-ferroceneethyl)maleimide (FEM) is introduced as an electroactive derivatizing agent for thiol functionalities in proteins. Using appropriate reaction conditions, the derivatization is completed within five minutes and no unspecific labeling of free amino functions is observed. Liquid chromatography/electrochemistry/mass spectrometry was used to detect the reaction products. The reagent is a useful tool for determining the number of free thiol groups or the total number of free and disulfide-bound thiol groups in proteins. The electrochemical cell provides additional information, because the increase in mass spectrometric response upon electrochemical oxidation of the neutral ferrocene to the charged ferrocinium groups is monitored. The method was successfully applied to the analysis of native proteins and their tryptic digests.

  5. Metabolite identification of a radiotracer by electrochemistry coupled to liquid chromatography with mass spectrometric and radioactivity detection.

    PubMed

    Baumann, Anne; Faust, Andreas; Law, Marylin P; Kuhlmann, Michael T; Kopka, Klaus; Schäfers, Michael; Karst, Uwe

    2011-07-01

    Radioligands, which specifically bind to a receptor or enzyme (target), enable molecular imaging of the target expression by positron emission tomography (PET). One very promising PET tracer is (S)-1-(4-(2-[(18)F]-fluoroethoxy)benzyl)-5-[1-(2-methoxymethylpyrrolidinyl)sulfonyl]isatin (isatin), a caspase-3 inhibitor, which has been developed at the University Hospital of Münster to image cell death (apoptosis). The translation of this novel tracer from preclinical evaluation to clinical examinations requires biodistribution studies, which characterize the pharmakodynamics and metabolic fate of the compound. This information is used to further optimize the radioligands and to interpret radioactive signals from tissues upon injection of the radioligand in vivo with respect to their specificity. The analysis of the metabolism of radioligands is hampered by the low amount of the compound being typically injected (nano/picomolar amount per injection). In the present study, electrochemistry (EC) is applied to elucidate the oxidative metabolism pathway of the radiotracer. Previous studies have demonstrated that EC can be utilized as a complementary tool to conventional in vitro approaches in drug metabolism studies. Thereby, potential oxidative metabolites of the isatin are determined by EC coupled to electrospray ionization mass spectrometry (EC/ESI-MS). Moreover, using EC/liquid chromatography (LC) and ESI-ion trap MS(n), structural elucidation of the oxidation products is performed. Comparatively to EC, in vitro metabolism studies with rat liver microsomes are conducted. Finally, the developed LC/ESI-MS method is applied to determine metabolites in body fluids and cell extracts from in vivo studies with the nonradioactive ((19)F) and radioactive isatin ((18)F). On the basis of the electrochemically generated oxidation products of the radioligand, the major radioactive metabolite occurring in vivo was successfully identified.

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

    PubMed

    Nasir, Muhammad Zafir Mohamad; Pumera, Martin

    2016-10-12

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

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

    SciTech Connect

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

    2012-04-30

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

  8. Electrochemistry of Sulfur Dioxide in Nonaqueous Solutions. Part I.

    DTIC Science & Technology

    1981-05-18

    Bowser I L. Burris 1 N. Issacs 1 9700 South Cass Avenue F. Tepper Argonne, IL 60439 1421 Clarkview Road Baltimore, MD 21209 John Hopkins Applied Physics... Newton , MA 02158 I4 46 . . ; ... . .. • NSWC TR 80-533 DISTRIBUTION (Cont.) Copies Copies Eagle-Picher Industries, Inc. Honeywell, Inc. Attn: D. R...Oak Street Beverly, MA 01915 Newton , MA 02164 a, 48 V NSWC Ti qO-533 DISTRIDUTION (Cont.) Copies Copies RAY-O-VAC University of Maryland Attn: R

  9. Electrochemistry in hollow-channel paper analytical devices.

    PubMed

    Renault, Christophe; Anderson, Morgan J; Crooks, Richard M

    2014-03-26

    In the present article we provide a detailed analysis of fundamental electrochemical processes in a new class of paper-based analytical devices (PADs) having hollow channels (HCs). Voltammetry and amperometry were applied under flow and no flow conditions yielding reproducible electrochemical signals that can be described by classical electrochemical theory as well as finite-element simulations. The results shown here provide new and quantitative insights into the flow within HC-PADs. The interesting new result is that despite their remarkable simplicity these HC-PADs exhibit electrochemical and hydrodynamic behavior similar to that of traditional microelectrochemical devices.

  10. Exploiting the versatility and selectivity of Mo enzymes with electrochemistry.

    PubMed

    Bernhardt, Paul V

    2011-02-14

    This article covers recent advances in the electrochemical study of the mononuclear molybdenum enzymes. Virtually all of these enzymes catalyse a coupled 2-electron, O-atom transfer reaction on a substrate of either organic or inorganic origin. There is a remarkable commonality in structure, function and mechanism of the mononuclear Mo enzymes despite the diversity of their substrates; many that are important to environmental monitoring, food quality control and biomedical science. Mo enzymes routinely oxidise or reduce otherwise inert substrates for which there exist no rapid, simple and reliable analytical methods for their determination and as such represent a potentially rich source of proteins that may be applied in electrochemical biosensors.

  11. The application of electrochemistry to pharmaceutical stability testing--comparison with in silico prediction and chemical forced degradation approaches.

    PubMed

    Torres, Susana; Brown, Roland; Szucs, Roman; Hawkins, Joel M; Zelesky, Todd; Scrivens, Garry; Pettman, Alan; Taylor, Mark R

    2015-11-10

    The aim of this study was to evaluate the use of electrochemistry to generate oxidative degradation products of a model pharmaceutical compound. The compound was oxidized at different potentials using an electrochemical flow-cell fitted with a glassy carbon working electrode, a Pd/H2 reference electrode and a titanium auxiliary electrode. The oxidative products formed were identified and structurally characterized by LC-ESI-MS/MS using a high resolution Q-TOF mass spectrometer. Results from electrochemical oxidation using electrolytes of different pH were compared to those from chemical oxidation and from accelerated stability studies. Additionally, oxidative degradation products predicted using an in silico commercially available software were compared to those obtained from the various experimental methods. The electrochemical approach proved to be useful as an oxidative stress test as all of the final oxidation products observed under accelerated stability studies could be generated; previously reported reactive intermediate species were not observed most likely because the electrochemical mechanism differs from the oxidative pathway followed under accelerated stability conditions. In comparison to chemical degradation tests electrochemical degradation has the advantage of being much faster and does not require the use of strong oxidizing agents. Moreover, it enables the study of different operating parameters in short periods of time and optimisation of the reaction conditions (pH and applied potential) to achieve different oxidative products mixtures. This technique may prove useful as a stress test condition for the generation of oxidative degradation products and may help accelerate structure elucidation and development of stability indicating analytical methods.

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

    PubMed

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

    2013-03-15

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

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

    NASA Astrophysics Data System (ADS)

    Dhanda, Abhishek

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

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

    PubMed

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

    2009-11-15

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

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

    PubMed

    Wigger, Tina; Seidel, Albrecht; Karst, Uwe

    2017-02-27

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

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

    ERIC Educational Resources Information Center

    Osman, Kamisah; Lee, Tien Tien

    2014-01-01

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

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

    ERIC Educational Resources Information Center

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

    2016-01-01

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

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

    ERIC Educational Resources Information Center

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

    2016-01-01

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

  19. Atomic-scale electrochemistry on the surface of a manganite

    SciTech Connect

    Vasudevan, Rama K.; Tselev, Alexander; Baddorf, Arthur P.; Kalinin, Sergei V.

    2015-04-09

    The doped manganese oxides (manganites) have been widely studied for their colossal magnetoresistive effects, for potential applications in oxide spintronics, electroforming in resistive switching devices, and are materials of choice as cathodes in modern solid oxide fuel cells. However, little experimental knowledge of the dynamics of the surfaces of perovskite manganites at the atomic scale exists. Here, through in-situ scanning tunnelling microscopy (STM), we demonstrate atomic resolution on samples of La0.625Ca0.375MnO3 grown on (001) SrTiO3 by pulsed laser deposition (PLD). Furthermore, by applying triangular DC waveforms of increasing amplitude to the STM tip, and measuring the tunnelling current, we demonstrate the ability to both perform and monitor surface electrochemical processes at the atomic level, including, for the first time in a manganite, formation of single and multiple oxygen vacancies, disruption of the overlying manganite layers, and removal and deposition of individual atomic units or clusters. Our work paves the way for better understanding of surface oxygen reactions in these systems.

  20. Assessment of insulated conductive cantilevers for biology and electrochemistry

    NASA Astrophysics Data System (ADS)

    Frederix, Patrick L. T. M.; Gullo, Maurizio R.; Akiyama, Terunobu; Tonin, Andreas; de Rooij, Nicolaas F.; Staufer, Urs; Engel, Andreas

    2005-08-01

    This paper describes the characterization and application of electrically insulated conductive tips mounted on a cantilever for use in an atomic force microscope and operated in liquid. These multifunctional probes were microfabricated and designed for measurements on biological samples in buffer solution, but they can also be employed for electrochemical applications, in particular scanning electrochemical microscopy. The silicon nitride based cantilevers had a spring constant <=0.1 N m-1 and a conductive tip, which was insulated except at the apex. The conductive core of the tip consisted of a metal, e.g. platinum silicide, and exhibited a typical radius of 15 nm. The mechanical and electrical characterization of the probe is presented and discussed. First measurements on the hexagonally packed intermediate layer of Deinococcus radiodurans demonstrated the possibility to adjust the image contrast by applying a voltage between a support and the conductive tip and to measure variations of less than 1 pA in faradaic current with a lateral resolution of 7.8 nm.

  1. Atomic-scale electrochemistry on the surface of a manganite

    DOE PAGES

    Vasudevan, Rama K.; Tselev, Alexander; Baddorf, Arthur P.; ...

    2015-04-09

    The doped manganese oxides (manganites) have been widely studied for their colossal magnetoresistive effects, for potential applications in oxide spintronics, electroforming in resistive switching devices, and are materials of choice as cathodes in modern solid oxide fuel cells. However, little experimental knowledge of the dynamics of the surfaces of perovskite manganites at the atomic scale exists. Here, through in-situ scanning tunnelling microscopy (STM), we demonstrate atomic resolution on samples of La0.625Ca0.375MnO3 grown on (001) SrTiO3 by pulsed laser deposition (PLD). Furthermore, by applying triangular DC waveforms of increasing amplitude to the STM tip, and measuring the tunnelling current, we demonstratemore » the ability to both perform and monitor surface electrochemical processes at the atomic level, including, for the first time in a manganite, formation of single and multiple oxygen vacancies, disruption of the overlying manganite layers, and removal and deposition of individual atomic units or clusters. Our work paves the way for better understanding of surface oxygen reactions in these systems.« less

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

    PubMed

    Dimcheva, Nina; Horozova, Elena

    2013-04-01

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

  3. Na-Ion Battery Anodes: Materials and Electrochemistry.

    PubMed

    Luo, Wei; Shen, Fei; Bommier, Clement; Zhu, Hongli; Ji, Xiulei; Hu, Liangbing

    2016-02-16

    also outlined, where graphene oxide was employed as dehydration agent and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was used to unzip wood fiber. Furthermore, surface modification by atomic layer deposition technology is introduced, where we discover that a thin layer of Al2O3 can function to encapsulate Sn nanoparticles, leading to a much enhanced cycling performance. We also highlight recent work about the phosphorene/graphene anode, which outperformed other anodes in terms of capacity. The aromatic organic anode is also studied as anode with very high initial sodiation capacity. Furthermore, electrochemical intercalation of Na ions into reduced graphene oxide is applied for fabricating transparent conductors, demonstrating the great feasibility of Na ion intercalation for optical applications.

  4. Electrochemistry-mass spectrometry for in-vitro determination of selected chemotherapeutics and their electrochemical products in comparison to in-vivo approach.

    PubMed

    Szultka-Mlynska, Malgorzata; Buszewski, Boguslaw

    2016-11-01

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

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

    PubMed Central

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

    2017-01-01

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

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

    PubMed

    Popat, Sudeep C; Torres, César I

    2016-09-01

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

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

    PubMed

    Termebaf, Hajar; Shayan, Mohsen; Kiani, Abolfazl

    2015-12-08

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

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

    NASA Astrophysics Data System (ADS)

    Scholz, Fritz; Schröder, Uwe; Gulaboski, Rubin

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

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

    PubMed

    Torres, César Iván

    2014-06-01

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

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

    NASA Astrophysics Data System (ADS)

    Tucceri, R.

    2004-12-01

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

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

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1994-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed

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

    2014-08-07

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

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

    SciTech Connect

    Osseo-Asare, K.

    1992-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

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

    PubMed

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

    2013-09-05

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

  18. Structural properties and electrochemistry of α-LiFeO2

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

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

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

    PubMed

    Chivers, Tristram; Elder, Philip J W

    2013-07-21

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

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

    PubMed

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

    2009-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

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

    PubMed

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

    2003-10-15

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

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

    PubMed

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

    2010-03-15

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

  5. Electrochemistry for the generation of renewable chemicals: One-pot electrochemical deoxygenation of xylose to δ-valerolactone.

    PubMed

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

    2017-03-22

    In this study, we demonstrate the electrochemical conversion of xylose to δ-valerolactone via carbonyl intermediates. The conversion was achieved in aqueous media and at ambient conditions. This study also demonstrates that feedstocks for the use of electrochemistry for production of renewable chemicals and biofuels can be extended to primary carbohydrate molecules. This is the first report on a one-pot electrochemical deoxygenation of xylose to δ-valerolactone.

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

    PubMed

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

    2009-01-01

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

  7. Application of on-line electrochemistry/electrospray/tandem mass spectrometry to a quantification method for the antipsychotic drug zotepine in human serum.

    PubMed

    Nozaki, Kazuyoshi; Osaka, Issey; Kawasaki, Hideya; Arakawa, Ryuichi

    2009-10-01

    A simple, rapid, and sensitive on-line liquid chromatographic electrochemistry/electrospray/tandem mass spectrometry (LC-EC/ESI-MS/MS) method for the determination of zotepine in human serum was developed using a new generated-electrochemically fragment ion, and was validated. A recent novel technique of LC-EC/ESI-MS/MS that combines LC-MS/MS and the on-line EC reaction is potentially applicable to developing a quantification method for drugs in biological samples. Newly formed products generated by the on-line EC cell are expected to provide appropriate precursor and product ions for the MS/MS determination method. This technique was successfully applied to a drug assay in a biological matrix. After adding imipramine (IS) to a 30-microL aliquot of human serum, the resulting sample was simply deproteinated with acetonitrile for a measurement. The analytical run time was 5 min. The calibration curve was linear in the concentration range of 10-2000 ng/mL. The intra-assay precision and accuracy were in the range of 1.8-8.9 and 98.4-113%, respectively.

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

    NASA Astrophysics Data System (ADS)

    Ryan, David Martin

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

  9. Scopus: A system for the evaluation of scientific journals

    NASA Astrophysics Data System (ADS)

    Guz, A. N.; Rushchitsky, J. J.

    2009-04-01

    The paper discusses the evaluation of scientific journals based on the Scopus database, information tools, and criteria. The SJR (SCImago Journal Rank) as the main criterion used by Scopus to evaluate scientific journals is considered. The Scopus and ISI systems are compared using information on the journal Prikladnaya Mekhanika ( International Applied Mechanics), a number of world-known journals on mechanics, and some journals on natural sciences issued by the National Academy of Sciences of Ukraine. Some comments and proposals are formulated. This paper may be considered as a follow up on papers published in Prikladnaya Mekhanika ( International Applied Mechanics) in 2005-2009

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    2015-02-15

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

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

    SciTech Connect

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

    2010-12-15

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

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

    PubMed

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

    2016-01-21

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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

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

    SciTech Connect

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

    2009-11-01

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

  17. Wireless Synthesis and Activation of Electrochemiluminescent Thermoresponsive Janus Objects Using Bipolar Electrochemistry.

    PubMed

    Phuakkong, Oranit; Sentic, Milica; Li, Haidong; Warakulwit, Chompunuch; Limtrakul, Jumras; Sojic, Neso; Kuhn, Alexander; Ravaine, Valérie; Zigah, Dodzi

    2016-12-13

    In this work, bipolar electrochemistry (BPE) is used as a dual wireless tool to generate and to activate a thermoresponsive electrochemiluminescent (ECL) Janus object. For the first time, BPE allows regioselective growth of a poly(N-isopropylacrylamide) (pNIPAM) hydrogel film on one side of a carbon fiber. It is achieved thanks to the local reduction of persulfate ions, which initiate radical polymerization of NIPAM. By controlling the electric field and the time of the bipolar electrochemical reactions, we are able to control the length and the thickness of the deposit. The resulting pNIPAM film is found to be swollen in water at room temperature and collapsed when heated above 32 °C. We further incorporated a covalently attached ruthenium complex luminophore, Ru(bpy)3(2+), in the hydrogel film. In the second time, BPE is used to activate remotely the electrogenerated chemiluminescence (ECL) of the Ru(bpy)3(2+) moieties in the film. We take advantage of the film responsiveness to amplify the ECL signal. Upon collapse of the film, the ECL signal, which is sensitive to the distance between adjacent Ru(bpy)3(2+) centers, is strongly amplified. It is therefore shown that BPE is a versatile tool to generate highly sophisticated materials based on responsive polymers, which could lead to sensitive sensors.

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

    DOE PAGES

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

    2016-04-20

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

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

    PubMed

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

    2014-08-15

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

  20. Water as a promoter and catalyst for dioxygen electrochemistry in aqueous and organic media.

    SciTech Connect

    Staszak-Jirkovsky, Jakub; Subbaraman, Ram; Strmcnik, Dusan; Harrison, Katherine L.; Diesendruck, Charles E.; Assary, Rajeev; Frank, Otakar; Kobr, Lukas; Wiberg, Gustav K.H; Genorio, Bostjan; Connell, Justin G.; Lopes, Pietro P.; Stamenkovic, Vojislav R.; Curtiss, Larry; Moore, Jeffrey S.; Zavadil, Kevin R.; Markovic, Nenad M.

    2015-11-01

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

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

    SciTech Connect

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

    1995-12-31

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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

    Karimi, Anahita; Hayat, Akhtar; Andreescu, Silvana

    2017-01-15

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

  4. Electrohydrodynamic jet printing and a preliminary electrochemistry test of graphene micro-scale electrodes

    NASA Astrophysics Data System (ADS)

    Wang, Dazhi; Zha, Wen; Feng, Li; Ma, Qian; Liu, Xianming; Yang, Ning; Xu, Zheng; Zhao, Xiaojun; Liang, Junsheng; Ren, Tongqun; Wang, Xiaodong

    2016-04-01

    This paper reports the use of electrohydrodynamic jet (E-jet) printing technique for producing a wide range of graphene micro-scale structures. Ethyl cellulose-dispersed graphene ink and Nafion-dispersed graphene ink were prepared and used for E-Jet printing. A glass slide and PDMS substrate were used for E-Jet printing of graphene ink. The E-jet printed graphene micro-scale structures using ethyl cellulose-dispersed graphene ink presented a feature of center arrayed graphene surrounded by the track of evaporated solution. However, the E-Jet printed graphene structures using Nafion-dispersed graphene ink exhibited uniform arranged features. It was observed that the resistivity of the graphene structures printed from the ethyl cellulose-dispersed graphene ink was much lower than that from the Nafion-dispersed graphene ink. In addition, the graphene micro-scale electrodes were E-Jet printed for preliminary electrochemical applications. The results showed that the graphene micro-scale electrodes had a distinct response for the lead ion. Furthermore, a Pt/graphene composite electrode was formed and an electrochemistry test was conducted. It was found that the Pt /graphene composite electrode had a more sensitive response compared with the pure Pt electrode for electrochemical sensing.

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

    PubMed

    Cumba, Loanda R; Kolliopoulos, Athanasios V; Smith, Jamie P; Thompson, Paul D; Evans, Peter R; Sutcliffe, Oliver B; do Carmo, Devaney R; Banks, Craig E

    2015-08-21

    "Synthacaine" is a New Psychoactive Substance which is, due to its inherent psychoactive properties, reported to imitate the effects of cocaine and is therefore consequently branded as "legal cocaine". The only analytical approach reported to date for the sensing of "Synthacaine" is mass spectrometry. In this paper, we explore and evaluate a range of potential analytical techniques for its quantification and potential use in the field screening "Synthacaine" using Raman spectroscopy, presumptive (colour) testing, High Performance Liquid Chromatography (HPLC) and electrochemistry. HPLC analysis of street samples reveals that "Synthacaine" comprises a mixture of methiopropamine (MPA) and 2-aminoindane (2-AI). Raman spectroscopy and presumptive (colour) tests, the Marquis, Mandelin, Simon's and Robadope test, are evaluated towards a potential in-the-field screening approach but are found to not be able to discriminate between the two when they are both present in the same sample, as is the case in the real street samples. We report for the first time a novel indirect electrochemical protocol for the sensing of MPA and 2-AI which is independently validated in street samples with HPLC. This novel electrochemical approach based upon one-shot disposable cost effective screen-printed graphite macroelectrodes holds potential for in-the-field screening for "Synthacaine".

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

    PubMed

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

    2012-11-01

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

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

    PubMed

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

    2014-02-01

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

  8. Applied Stratigraphy

    NASA Astrophysics Data System (ADS)

    Lucas, Spencer G.

    Stratigraphy is a cornerstone of the Earth sciences. The study of layered rocks, especially their age determination and correlation, which are integral parts of stratigraphy, are key to fields as diverse as geoarchaeology and tectonics. In the Anglophile history of geology, in the early 1800s, the untutored English surveyor William Smith was the first practical stratigrapher, constructing a geological map of England based on his own applied stratigraphy. Smith has, thus, been seen as the first “industrial stratigrapher,” and practical applications of stratigraphy have since been essential to most of the extractive industries from mining to petroleum. Indeed, gasoline is in your automobile because of a tremendous use of applied stratigraphy in oil exploration, especially during the latter half of the twentieth century. Applied stratigraphy, thus, is a subject of broad interest to Earth scientists.

  9. Applied oceanography

    SciTech Connect

    Bishop, J.M.

    1984-01-01

    This book combines oceanography principles and applications such as marine pollution, resources, and transportation. It is divided into two main parts treating the basic principles of physical oceanography, and presenting a unique systems framework showing how physical oceanography, marine ecology, economics, and government policy may be combined to define the newly developing field of applied oceanography.

  10. Applied Enzymology.

    ERIC Educational Resources Information Center

    Manoharan, Asha; Dreisbach, Joseph H.

    1988-01-01

    Describes some examples of chemical and industrial applications of enzymes. Includes a background, a discussion of structure and reactivity, enzymes as therapeutic agents, enzyme replacement, enzymes used in diagnosis, industrial applications of enzymes, and immobilizing enzymes. Concludes that applied enzymology is an important factor in…

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

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-02-01

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

  12. Semiconductor electrochemistry of coal pyrite. Technical progress report, April--June 1992

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1992-12-01

    Pyrite synthesis is of interest in many diverse fields, such as geology, fuel processing technology, chemistry, metallurgy, materials science, and so on. Based on fundamental studies of this process, the formation mechanisms of this important sulfide on the earth can be better understood. The studies can also help us to better understand the surface chemistry and electrochemistry of pyrite, thereby assisting in the development of more efficient processes for removal of the sulfide from coal. The work performed during this quarter focuses on the study of the reaction between aqueous sulfide ions and dissolved Fe(II) salts by using a stopped-flow spectrophotometric technique. At a wavelength of 500 mn, no absorption was observed with either aqueous sulfide or dissolved Fe(II) salt alone. However, when the two solutions were mixed, a strong absorbance appeared at the same wavelength. The absorbance-time curve showed that a black material formed at the first few seconds of the reaction, then this material decayed and changed gradually to a lighter dark material within the following several minutes. These processes were pH-dependent. It was more likely to form the black intermediate at the pH range from 7 to 8. This indicates that the reaction between Fe{sup 2+} and HS{sup {minus}} results in the formation of the black intermediate because in this pH range, both Fe{sup 2+} and HS{sup {minus}} are the predominant species. The absorbance varied linearly with the concentration of the reactant for the first step of the reaction. The absorptivity of the black intermediate was determined as 4800 l/mol/cm. By means of this spectrophotometric technique, the stoichiometry, the equilibrium constant and the rate constant of the reaction will be determined.

  13. Integrating bipolar electrochemistry and electrochemiluminescence imaging with microdroplets for chemical analysis.

    PubMed

    Wu, Suozhu; Zhou, Zhenyu; Xu, Linru; Su, Bin; Fang, Qun

    2014-03-15

    Here we develop a microdroplet sensor based on bipolar electrochemistry and electrochemiluminescence (ECL) imaging. The sensor was constructed with a closed bipolar cell on a hybrid poly(dimethylsioxane) (PDMS)-indium tin oxide (ITO) glass microchip. The ITO microband functions as the bipolar electrode and its two poles are placed in two spatially separate micro-reservoirs predrilled on the PDMS cover. After loading microliter-sized liquid droplets of tris(2,2'-bipyridyl) ruthenium (II)/2-(dibutylamino) ethanol (Ru(bpy)3(2+)/DBAE) and the analyte to the micro-reservoirs, an appropriate external voltage imposed on the driving electrodes could induce the oxidation of Ru(bpy)3(2+)/DBAE and simultaneous reduction of the analyte at the anodic and cathodic poles, respectively. ECL images generated by Ru(bpy)3(2+)/DBAE oxidation at the anodic pole and the electrical current flowing through the bipolar electrode can be recorded for quantitative analyte detection. Several types of quinones were selected as model analytes to demonstrate the sensor performance. Furthermore, the cathodic pole of bipolar electrode can be modified with (3-aminopropyl)triethoxysilane-gold nanoparticles-horseradish peroxidase composites for hydrogen peroxide detection. This microdroplet sensor with a closed bipolar cell can avoid the interference and cross-contamination between analyte solutions and ECL reporting reagents. It is also well adapted for chemical analysis in the incompatible system, e.g., detection of organic compounds insoluble in water by aqueous ECL generation. Moreover, this microdroplet sensor has advantages of simple structure, high sensitivity, fast response and wide dynamic response, providing great promise for chemical and biological analysis.

  14. Recent Advances in Modeling Transition Metal Oxides for Photo-electrochemistry

    NASA Astrophysics Data System (ADS)

    Caspary Toroker, Maytal

    Computational research offers a wide range of opportunities for materials science and engineering, especially in the energy arena where there is a need for understanding how material composition and structure control energy conversion, and for designing materials that could improve conversion efficiency. Potential inexpensive materials for energy conversion devices are metal oxides. However, their conversion efficiency is limited by at least one of several factors: a too large band gap for efficiently absorbing solar energy, similar conduction and valence band edge characters that may lead to unfavorably high electron-hole recombination rates, a valence band edge that is not positioned well for oxidizing water, low stability, low electronic conductivity, and low surface reactivity. I will show how we model metal oxides with ab-initio methods, primarily DFT +U. Our previous results show that doping with lithium, sodium, or hydrogen could improve iron (II) oxide's electronic properties, and alloying with zinc or nickel could improve iron (II) oxide's optical properties. Furthermore, doping nickel (II) oxide with lithium could improve several key properties including solar energy absorption. In this talk I will highlight new results on our understanding of the mechanism of iron (III) oxide's surface reactivity. Our theoretical insights bring us a step closer towards understanding how to design better materials for photo-electrochemistry. References: 1. O. Neufeld and M. Caspary Toroker, ``Pt-doped Fe2O3 for enhanced water splitting efficiency: a DFT +U study'', J. Phys. Chem. C 119, 5836 (2015). 2. M. Caspary Toroker, ``Theoretical Insights into the Mechanism of Water Oxidation on Non-stoichiometric and Ti - doped Fe2O3 (0001)'', J. Phys. Chem. C, 118, 23162 (2014). This research was supported by the Morantz Energy Research Fund, the Nancy and Stephen Grand Technion Energy Program, the I-CORE Program of the Planning and Budgeting Committee, and The Israel Science

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

    PubMed

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

    2015-10-01

    The feedstocks for biochar production are diverse and many of them contain various minerals in addition to being rich in carbon. Twelve types of biomass classified into 2 categories: plant-based and municipal waste, were employed to produce biochars under 350 °C and 500 °C. Their pH, point of zero net charge (PZNC), zeta potential, cation and anion exchange capacity (CEC and AEC) were analyzed. The municipal waste-based biochars (MW-BC) had higher mineral levels than the plant-based biochars (PB-BC). However, the water soluble mineral levels were lower in the MW-BCs due to the dominant presence of less soluble minerals, such as CaCO3 and (Ca,Mg)3(PO4)2. The higher total minerals in MW-BCs accounted for the higher PZNC (5.47-9.95) than in PB-BCs (1.91-8.18), though the PZNCs of the PB-BCs increased more than that of the MW-BCs as the production temperature rose. The minerals had influence on the zeta potentials via affecting the negative charges of biochars and the ionic strength of solution. The organic functional groups in PB-BCs such as -COOH and -OH had a greater effect on the CEC and AEC, while the minerals had a greater effect on that of MW-BCs. The measured CEC and AEC values had a strong positive correlation with the total amount of soluble cations and anions, respectively. Results indicated that biochar surface charges depend not only on the organic functional groups, but also on the minerals present and to some extent, minerals have more influences on the surface electrochemistry and ion exchange properties of biochar.

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

    SciTech Connect

    Osseo-Asare, K.; Wei, Dawei

    1996-01-01

    This project seeks to advance the fundamental understanding of the physico-chemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. Central to this research is the use of synthetic microsize particles of pyrite as model microelectrodes to investigate the semiconductor electrochemistry of pyrite. The research focuses on: (a) the synthesis of microsize particles of pyrite in aqueous solution at room temperature, (b) the formation of iron sulfide complex, the precursor of FeS or FeS{sub 2}, and (c) the relationship between the semiconductor properties of pyrite and its interfacial electrochemical behavior in the dissolution process. In Chapter 2, 3 and 4, a suitable protocol for preparing microsize particles of pyrite in aqueous solution is given, and the essential roles of the precursors elemental sulfur and ``FeS`` in pyrite formation are investigated. In Chapter 5, the formation of iron sulfide complex prior to the precipitation of FeS or FeS{sub 2} is investigated using a fast kinetics technique based on a stopped-flow spectrophotometer. The stoichiometry of the iron sulfide complex is determined, and the rate and formation constants are also evaluated. Chapter 6 provides a summary of the semiconductor properties of pyrite relevant to the present study. In Chapters 7 and 8, the effects of the semiconductor properties on pyrite dissolution are investigated experimentally and the mechanism of pyrite dissolution in acidic aqueous solution is examined. Finally, a summary of the conclusions from this study and suggestions for future research are presented in Chapter 9.

  17. The Investigation and Characterization of the Group 3 [Nickel-Iron]-Hydrogenases Using Protein Film Electrochemistry

    NASA Astrophysics Data System (ADS)

    McIntosh, Chelsea Lee

    Hydrogenases, the enzymes that reversibly convert protons and electrons to hydrogen, are used in all three domains of life. [NiFe]-hydrogenases are considered best suited for biotechnological applications because of their reversible inactivation with oxygen. Phylogenetically, there are four groups of [NiFe]-hydrogenases. The best characterized group, "uptake" hydrogenases, are membrane-bound and catalyze hydrogen oxidation in vivo. In contrast, the group 3 [NiFe]-hydrogenases are heteromultimeric, bifunctional enzymes that fulfill various cellular roles. In this dissertation, protein film electrochemistry (PFE) is used to characterize the catalytic properties of two group 3 [NiFe]-hydrogenases: HoxEFUYH from Synechocystsis sp. PCC 6803 and SHI from Pyrococcus furiosus. First, HoxEFUYH is shown to be biased towards hydrogen production. Upon exposure to oxygen, HoxEFUYH inactivates to two states, both of which can be reactivated on the timescale of seconds. Second, we show that PfSHI is the first example of an oxygen tolerant [NiFe]-hydrogenase that produces two inactive states upon exposure to oxygen. Both inactive states are analogous to those characterized for HoxEFUYH, but oxygen exposed PfSHI produces a greater fraction that reactivates at high potentials, enabling hydrogen oxidation in the presence of oxygen. Third, it is shown that removing the NAD(P)-reducing subunits from PfSHI leads to a decrease in bias towards hydrogen oxidation and renders the enzyme oxygen sensitive. Both traits are likely due to impaired intramolecular electron transfer. Mechanistic hypotheseses for these functional differences are considered.

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

    PubMed

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

    2013-10-15

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

  19. Structural evolution and electrochemistry of monoclinic NaNiO2 upon the first cycling process

    NASA Astrophysics Data System (ADS)

    Han, Man Huon; Gonzalo, Elena; Casas-Cabanas, Montse; Rojo, Teófilo

    2014-07-01

    Electrochemistry and structural evolution of monoclinic NaNiO2 as a cathode material for Na-ion battery is reported. The initial charge capacity reached 160 mA h g-1 and the following discharge capacity of 114.6 mA h g-1, within the voltage range of 4.0-1.5 V at C/10. The multiple phase transition leading to O‧3, P‧3, P″3, O″3, and O‴3 stacking types (NaNiO2, Na0.91NiO2, Na0.84NiO2, Na0.81NiO2 and Na0.79NiO2 transitions, respectively, according to a previous report) during the 1st charge/discharge process is analysed using ex situ and in situ XRD techniques, and the stoichiometry of each phase is herein revised. The charge/discharge profile shows a highly reversible nature of the cathode, except that fully sodiated phase could not be achieved at the subsequent discharge. Two new phases have been discovered: a monoclinic O3 structure (designated as O⁗3) at the beginning of the charge (and end of discharge) and a P3 structure (designated as P‴3) at 3.38 V that appeared only during the charge process. The composition of the new O⁗3-phase corresponds to Na0.83NiO2, which is the closest to the fully sodiated phase at room temperature achieved during the discharge process reported up to date, and the composition of the new P‴3-phase corresponds approximately to Na0.50NiO2.

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

    PubMed

    Ma, Xiao; Jia, Li; Zhang, Lu; Zhu, Liande

    2014-04-01

    Carbon nanotubes (CNTs) have been widely employed as electrode materials in diverse branches of electrochemistry, which are claimed to display dramatically improved electrochemical behaviour compared to the conventional carbon materials. But a series of recent publications have demonstrated that the electrocatalysis of CNTs might be due to the presence of some impurities, such as metallic catalysts, nanographitic particles and amorphous carbon. For this reason, CNTs are usually purified or treated with nitric acid or nitric and sulphuric acid prior to their versatile applications. However, the strong acidic and oxidative conditions are so aggressive that serious erosion of the tube structures has inevitably taken place, which creates defects on the sidewalls and gives rise to numerous molecular byproducts, commonly referred as carboxylated carbonaceous fragments (CCFs). The adsorption of CCFs on CNTs greatly alters the surface conditions of CNTs which may significantly impact on their electrochemical properties. To this end, we wish to disclose whether the electrocatalysis of the nitric acid purified CNTs is affected by the adsorption of the CCFs. Ascorbic acid (AA) and β-nicotinamide adenine dinucleotide (NADH) as selected as the targeting benchmarks that are known to be insensitive to the presence of metallic impurities, which may guarantee the preclusion of the promoting contributions from the metallic catalysts resident in CNTs. We have demonstrated that the electrocatalytic activities of the CNTs are actually dominated by the adsorbed CCFs generated during the acidic pre-treatment. After removal of the CCFs by base rinse, the electrocatalytic properties of CNTs are greatly deteriorated and degraded to the level similar to the conventional graphite powder. We believe this finding is particularly meaningful to uncover the mysterious electrocatalysis of CNTs.

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

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1993-05-01

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

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

    PubMed

    Cai, Yi; Zheng, Qiuling; Liu, Yong; Helmy, Roy; Loo, Joseph A; Chen, Hao

    2015-01-01

    This study presents the development of ultra-performance liquid chromatography (UPLC) mass spectrometry (MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of proteins/peptides that contain disulfide bonds. In our approach, a protein/peptide mixture sample undergoes a fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and tandem mass spectrometry (MS/MS) analyses. The electrochemical cell is coupled to the mass spectrometer using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, peptides that contain disulfide bonds can be differentiated from those without disulfide bonds, as the former are electroactive and reducible. MS/MS analysis of the disulfide-reduced peptide ions provides increased information on the sequence and disulfide-linkage pattern. In a reactive DESI- MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which will be useful in top- down protein structure MS analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1(~)2 orders of magnitude by using UPLC for the liquid chromatography (LC)/EC/MS platform, in comparison to the previously used high- performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion, and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis.

  3. Applied Nanotoxicology

    PubMed Central

    Hobson, David W.; Roberts, Stephen M.; Shvedova, Anna A.; Warheit, David B.; Hinkley, Georgia K.; Guy, Robin C.

    2016-01-01

    Nanomaterials, including nanoparticles and nanoobjects, are being incorporated into everyday products at an increasing rate. These products include consumer products of interest to toxicologists such as pharmaceuticals, cosmetics, food, food packaging, household products, and so on. The manufacturing of products containing or utilizing nanomaterials in their composition may also present potential toxicologic concerns in the workplace. The molecular complexity and composition of these nanomaterials are ever increasing, and the means and methods being applied to characterize and perform useful toxicologic assessments are rapidly advancing. This article includes presentations by experienced toxicologists in the nanotoxicology community who are focused on the applied aspect of the discipline toward supporting state of the art toxicologic assessments for food products and packaging, pharmaceuticals and medical devices, inhaled nanoparticle and gastrointestinal exposures, and addressing occupational safety and health issues and concerns. This symposium overview article summarizes 5 talks that were presented at the 35th Annual meeting of the American College of Toxicology on the subject of “Applied Nanotechnology.” PMID:26957538

  4. Conceptual difficulties experienced by senior high school students of electrochemistry: Electric circuits and oxidation-reduction equations

    NASA Astrophysics Data System (ADS)

    Garnett, Pamela J.; Treagust, David F.

    The purpose of this research was to investigate students' understanding of electrochemistry following a course of instruction. A list of conceptual and propositional knowledge statements was formulated to identify the knowledge base necessary for students to understand electric circuits and oxidation-reduction equations. The conceptual and propositional knowledge statements provided the framework for the development of a semistructured interview protocol which was administered to 32 students in their final year of high school chemistry. The interview questions about electric circuits revealed that several students in the sample were confused about the nature of electric current both in metallic conductors and in electrolytes. Students studying both physics and chemistry were more confused about current flow in metallic conductors than students who were only studying chemistry. In the section of the interview which focused on oxidation and reduction, many students experienced problems in identifying oxidation-reduction equations. Several misconceptions relating to the inappropriate use of definitions of oxidation and reduction were identified. The data illustrate how students attempted to make sense of the concepts of electrochemistry with the knowledge they had already developed or constructed. The implications of the research are that teachers, curriculum developers, and textbook writers, if they are to minimize potential misconceptions, need to be cognizant of the relationship between physics and chemistry teaching, of the need to test for erroneous preconceptions about current before teaching about electrochemical (galvanic) and electrolytic cells, and of the difficulties experienced by students when using more than one model to explain scientific phenomena.

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

    PubMed

    Liu, Chuan-Yin; Hu, Ji-Ming

    2009-03-15

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

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

    PubMed

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

    2009-10-15

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

  7. Li/Ag2VO2PO4 batteries: the roles of composite electrode constituents on electrochemistry

    SciTech Connect

    Bock, David C.; Bruck, Andrea M.; Pelliccione, Christopher J.; Zhang, Yiman; Takeuchi, Kenneth J.; Marschilok, Amy C.; Takeuchi, Esther S.

    2016-11-01

    Silver vanadium phosphorous oxide, Ag2V2OPO4, was used as a model system to systematically study the impact on the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Three different electrode compositions were investigated.

  8. A new family of multiferrocene complexes with enhanced control of structure and stoichiometry via coordination-driven self-assembly and their electrochemistry.

    PubMed

    Yang, Hai-Bo; Ghosh, Koushik; Zhao, Yue; Northrop, Brian H; Lyndon, Matthew M; Muddiman, David C; White, Henry S; Stang, Peter J

    2008-01-23

    The design and synthesis of a new family of multiferrocene complexes with enhanced control of structure and stoichimetry via coordination-driven self-assembly is described. Insight into the structure and electronic properties of all supramolecules was obtained by electrochemical studies. The collective results provide an enhanced understanding of the influence of structural factors on the electrochemistry of multifunctional electroactive supramolecular architectures.

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

    PubMed

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

    2013-05-21

    Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of

  10. Carbon MEMS from the nanoscale to the macroscale: Novel fabrication techniques and applications in electrochemistry

    NASA Astrophysics Data System (ADS)

    Zaouk, Rabih Bachir

    Dimensional C-MEMS batteries without the need for very complex multiphysics modeling. The results show that variations in current density distributions, previously reported in the literature, were exaggerated. The work then moves to describe two other novel multiscale C-MEMS fabrication techniques that attempt to bridge the gap between macro and nano scales. The first involves the combination of electrochemistry and photolithography in order to achieve fractal like structures made entirely of carbon. The second uses a solution based deposition technique that yields fine submicron glassy carbon wires suspended between microposts hundreds of microns apart. Although previously reported in the literature, the exact fabrication mechanism of these suspended nanowires was originally attributed to the wrong mechanism. The two phase flow deposition mechanism (i.e. stretching flow) is demonstrated and the original interpretation mechanism is rebutted. It is then shown how Carbon MEMS structures can be used in a multitude of applications, e.g. dielectrophoresis, selective trapping, particle separation and manipulation.

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

    PubMed

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

    2016-11-15

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

  12. Chemistry and electrochemistry of environment-assisted cracking of an aluminum-zinc-magnesium-copper alloy

    NASA Astrophysics Data System (ADS)

    Cooper, Kevin Richard

    2001-11-01

    The mechanism of environment-assisted cracking (EAC) of 7xxx-series alloys is unclear, involving uncertain contributions of hydrogen embrittlement (HE) and anodic dissolution (AD). Fundamental understanding of the EAC mechanism is lacking in part because the role of the crack environment is not well understood. The objective of this research was to characterize and understand the role of the crack chemistry and electrochemistry during aqueous EAC of AA 7050. The crack environment can differ significantly from bulk conditions. Cations, produced by AD, hydrolyze causing local acidification; anions from the bulk electrolyte concentrate within the crack to maintain charge neutrality; ohmic potential drop results from ion migration and diffusion. A positive correlation exists between da/dt and [Al3+]Tip in chromate-chloride electrolyte wherein tip dissolution dominates flank corrosion in establishing the crack chemistry. Tip pH was 2 to 4 and determined by the reaction Al3+ + H 2O = AlOH2+ + H+. The tip potential (ETip) was approximately -0.90 VSCE and independent of EApp . The low ETip and pH promote H+ reduction, generating atomic and molecular H. Hydrogen bubbles restrict ion movement, substantially increasing the effective crack resistance over bulk conditions. Absorbed atomic hydrogen facilitates HE. The spontaneous transition from slow, incubation to high-rate da/dt coincides with the establishment of a critical aggressive tip chemistry and tip depolarization. Development of the critical occluded chemistry necessary for accelerated da/dt is a competitive process between opposing forces: AD, hydrolysis and migration promote an aggressive environment whereas diffusion reduces concentration gradients, thereby retarding the formation of an aggressive chemistry. Quantitative assessment of the contribution of tip dissolution to crack advance is hindered by a lack of knowledge of two key parameters: the tip corrosion front height and the effective crack conductivity

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

    PubMed Central

    2016-01-01

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

  14. Applied geodesy

    SciTech Connect

    Turner, S.

    1987-01-01

    This volume is based on the proceedings of the CERN Accelerator School's course on Applied Geodesy for Particle Accelerators held in April 1986. The purpose was to record and disseminate the knowledge gained in recent years on the geodesy of accelerators and other large systems. The latest methods for positioning equipment to sub-millimetric accuracy in deep underground tunnels several tens of kilometers long are described, as well as such sophisticated techniques as the Navstar Global Positioning System and the Terrameter. Automation of better known instruments such as the gyroscope and Distinvar is also treated along with the highly evolved treatment of components in a modern accelerator. Use of the methods described can be of great benefit in many areas of research and industrial geodesy such as surveying, nautical and aeronautical engineering, astronomical radio-interferometry, metrology of large components, deformation studies, etc.

  15. Using electrochemistry - total internal refection imaging ellipsometry to monitor biochemical oxygen demand on the surface tethered polyelectrolyte modified electrode

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Sundararaman, Ravishankar; Weaver, Kendra; Arias, Tomas

    2012-02-01

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

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

    PubMed

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

    2017-01-06

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

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

    PubMed Central

    Wang, Wen-Cheng; Yan, Li-Jun; Shi, Fan; Niu, Xue-Liang; Huang, Guo-Lei; Zheng, Cai-Juan; Sun, Wei

    2015-01-01

    By using the hydrothermal method, carbon microspheres (CMS) were fabricated and used for electrode modification. The characteristics of CMS were investigated using various techniques. The biocompatible sensing platform was built by immobilizing hemoglobin (Hb) on the micrometer-sized CMS-modified electrode with a layer of chitosan membrane. On the cyclic voltammogram, a couple of quasi-reversible cathodic and anodic peaks appeared, showing that direct electrochemistry of Hb with the working electrode was achieved. The catalytic reduction peak currents of the bioelectrode to trichloroacetic acid was established in the linear range of 2.0~70.0 mmol·L−1 accompanied by a detection limit of 0.30 mmol·L−1 (3σ). The modified electrode displayed favorable sensitivity, good reproducibility and stability, which suggests that CMS is promising for fabricating third-generation bioelectrochemical sensors. PMID:26703621

  19. Further evidence for the quantum confined electrochemistry model of the formation mechanism of p - -type porous silicon

    NASA Astrophysics Data System (ADS)

    Jia, L.; Zang, S. L.; Wong, S. P.; Wilson, I. H.; Hark, S. K.; Liu, Z. F.; Cai, S. M.

    1996-11-01

    Two types of p- porous silicon (PS) were formed in HF solutions of different concentrations. One type with nanoscale (NS) dimensions of about 3 nm and the other with dimensions of about 5 nm. PS samples formed in the lower concentration of HF were anodized again in the higher concentration of HF and vice versa. The photoluminescence peak position and, thus, the size of NS units of PS were found to be related to the concentration of HF in which the PS is formed, independent of the forming time. The larger NS units of PS can be further electrochemically etched by anodization, while the smaller ones cannot. These results give a confirming evidence for the quantum confined electrochemistry model of the formation mechanism of PS based on the quantum confinement effect and classical electrochemical theory [S. L. Zhang, K. S. Ho, Y. T. Hou, B. D. Qian, P. Diao, and S. M. Cai, Appl. Phys. Lett. 62, 642 (1993)].

  20. Single nanowire electrode electrochemistry of silicon anode by in situ atomic force microscopy: solid electrolyte interphase growth and mechanical properties.

    PubMed

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

    2014-11-26

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

  1. Fast single run of vanilla fingerprint markers on microfluidic-electrochemistry chip for confirmation of common frauds.

    PubMed

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

    2009-10-01

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

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

    PubMed

    Shamsipur, Mojtaba; Tabrizi, Mahmoud Amouzadeh

    2014-12-01

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

  3. Li/Ag2VO2PO4 batteries: the roles of composite electrode constituents on electrochemistry

    DOE PAGES

    Bock, David C.; Bruck, Andrea M.; Pelliccione, Christopher J.; ...

    2016-11-01

    In this study, we utilize silver vanadium phosphorous oxide, Ag2VO2PO4, as a model system to systematically study the impact of the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Notably, although highly resistive, this bimetallic cathode can be discharged as a pure electroactive material in the absence of a conductive additive as it generates an in situ conductive matrix via a reduction displacement reaction resulting in the formation of silver metal nanoparticles. Also, three different electrode compositions were investigated: Ag2VO2PO4 only, Ag2VO2PO44 with binder, and Ag2VO2PO4 with binder and carbon. Constant current discharge, pulse testing andmore » impedance spectroscopy measurements were used to characterize the electrochemical properties of the electrodes as a function of depth of discharge. In situ EDXRD was used to spatially resolve the discharge progression within the cathode by following the formation of Ag0. Ex situ XRD and EXAFS modeling were used to quantify the amount of Ag0 formed. Results indicate that the metal center reduced (V5+ or Ag+) was highly dependent on composite composition (presence of PTFE, carbon), depth of discharge (Ag0 nanoparticle formation), and spatial location within the cathode. The addition of a binder was found to increase cell polarization, and the percolation network provided by the carbon in the presence of PTFE was further increased with reduction and formation of Ag0. Lastly, this study provides insight into the factors controlling the electrochemistry of resistive active materials in composite electrodes.« less

  4. In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

    SciTech Connect

    Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing; Laskin, Julia

    2016-11-07

    Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy. SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.

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

    PubMed

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

    2016-05-17

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

  6. Electrochemistry in Near-Critical and Supercritical Fluids. 4. Nitrogen Heterocycles, Nitrobenzene, and Solvated Electrons in Ammonia at Temperatures to 150C.

    DTIC Science & Technology

    1986-09-01

    of pyraz ne quinoxaline, phenazine and solvated electrons in near-critical and supercritical ammonia was investigated by cycU-i Voltanimetry and...Crooks and Allen J. Bard Department of Chemistry, University of Texas Austin, Texas 78712 ABSTRACT The electrochemistry of pyrazine, quinoxaline, phenazine ...in liquid ammonia at -40° C. The reductions of pyrazine, quinoxaline and phenazine at room temperature, and in the supercritical fluid (SCF), occur

  7. Experimental and theoretical study of possible correlation between the electrochemistry of canthin-6-one and the anti-proliferative activity against human cancer stem cells

    NASA Astrophysics Data System (ADS)

    Cebrián-Torrejón, G.; Doménech-Carbó, A.; Scotti, M. T.; Fournet, A.; Figadère, B.; Poupon, E.

    2015-12-01

    This work presents an approach to study the performance of novel targets able to overcome cancer stem cell chemoresistance, based on the voltammetric data for microparticulate films of natural or synthetic alkaloids from the canthin-6-one series. A comparison of this voltammetric technique with conventional solution phase electrochemistry suggests the differences in the anti-proliferative activity of canthin-6-ones could be tentatively correlated to their different capacity to generate semiquinone radical anions. These data also match theoretical calculations.

  8. Forensic electrochemistry applied to the sensing of new psychoactive substances: electroanalytical sensing of synthetic cathinones and analytical validation in the quantification of seized street samples.

    PubMed

    Smith, Jamie P; Metters, Jonathan P; Khreit, Osama I G; Sutcliffe, Oliver B; Banks, Craig E

    2014-10-07

    The electrochemical sensing of new psychoactive substance(s) (NPSs), synthetic cathinone derivatives also termed "legal highs", are explored with the use of metallic modified screen-printed electrochemical sensors (SPES). It is found that no significant electrochemical enhancement is evident with the use of either in situ bismuth or mercury film modified SPES compared to the bare underlying electrode substrate. In fact, the direct electrochemical reduction of the cathinone derivatives mephedrone (4-methylmethcathinone; 4-MMC) and 4'-methyl-N-ethylcathinone (4-methylethcathinone; 4-MEC) is found to be possible for the first time, without heavy metal catalysis, giving rise to useful voltammetric electroanalytical signatures in model aqueous buffer solutions. This novel electroanalytical methodology is validated toward the determination of cathinone derivatives (4-MMC and 4-MEC) in three seized street samples that are independently analyzed with high-performance liquid chromatography (HPLC) wherein excellent agreement between the two analytical protocols is found. Such an approach provides a validated laboratory tool for the quantification of synthetic cathinone derivatives and holds potential for the basis of a portable analytical sensor for the determination of synthetic cathinone derivatives in seized street samples.

  9. Silver Vanadium Diphosphate Ag2VP2O8: Electrochemistry and Characterization of Reduced Material providing Mechanistic Insights

    PubMed Central

    Takeuchi, Esther S.; Lee, Chia-Ying; Chen, Po-Jen; Menard, Melissa C.; Marschilok, Amy C.; Takeuchi, Kenneth J.

    2013-01-01

    Silver vanadium phosphorous oxides (AgwVxPyOz) are notable battery cathode materials due to their high energy density and demonstrated ability to form in-situ Ag metal nanostructured electrically conductive networks within the cathode. While analogous silver vanadium diphosphate materials have been prepared, electrochemical evaluations of these diphosphate based materials have been limited. We report here the first electrochemical study of a silver vanadium diphosphate, Ag2VP2O8, where the structural differences associated with phosphorous oxides versus diphosphates profoundly affect the associated electrochemistry. Reminiscent of Ag2VO2PO4 reduction, in-situ formation of silver metal nanoparticles was observed with reduction of Ag2VP2O8. However, counter to Ag2VO2PO4 reduction, Ag2VP2O8 demonstrates a significant decrease in conductivity upon continued electrochemical reduction. Structural analysis contrasting the crystallography of the parent Ag2VP2O8 with that of the proposed Li2VP2O8 reduction product is employed to gain insight into the observed electrochemical reduction behavior, where the structural rigidity associated with the diphosphate anion may be associated with the observed particle fracturing upon deep electrochemical reduction. Further, the diphosphate anion structure may be associated with the high thermal stability of the partially reduced Ag2VP2O8 materials, which bodes well for enhanced safety of batteries incorporating this material. PMID:25866419

  10. Conducting Polymer Nanostructures and Nanocomposites with Carbon Nanotubes: Hierarchical Assembly by Molecular Electrochemistry, Growth Aspects and Property Characterization.

    PubMed

    Gupta, Sanju; Price, Carson; Heintzman, Eli

    2016-01-01

    Conducting (or π-conjugated) polymers are promising materials for preparing supramolecular nano-structures and nanocomposites. We report controlled nanostructure syntheses of polypyrrole (PPy) and poylaniline (PANi) via electropolymerization (i.e., in-situ electrochemical anodic oxidation). The density, shape, caliber and thickness of self-assembled PPy micro-containers are regulated by electrochemical potential window for H2 bubbles and number of cyclic voltammetric (potentiodynamic) scans. Likewise, we employed amperometry, chronopotentiometry and potentiodynamic modes using hydrochloric acid as oxidizing agent to prepare PANi nanoparticles and nanotubules. We present our findings from the viewpoint of molecular electrochemistry with growth kinetic aspects yielding mechanistic details (initially forming dimers and oligomers as nucleating agents followed by polymer growth). Also targeted is forming nanocomposites with functionalized single- and multi-walled carbon nanotubes (FSWCNTs and FMWCNTs) as reinforced agent to optimize structural and functional properties. All of these novel nanomaterials are characterized using a range of complementary techniques to establish microscopic structure-property-function relationship.

  11. Impact of Soil Composition and Electrochemistry on Corrosion of Rock-cut Slope Nets along Railway Lines in China.

    PubMed

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

    2015-10-09

    Taking the slope of Suiyu Railway to study, the research separately studied soil resistivity, soil electrochemistry (corrosion potential, oxidization reduction potential, electric potential gradient and pH), soil anions (total soluble salt, Cl(-), SO4(2-) and ), and soil nutrition (moisture content, organic matter, total nitrogen, alkali-hydrolysable nitrogen, available phosphorus, and available potassium) at different slope levels, and conducted corrosion grade evaluation on artificial soil according to its single index and comprehensive indexes. Compared with other factors, water has the biggest impact on the corrosion of slope protection net, followed by anion content. Total soluble salt has the moderate impact on the corrosion of slope protection net, and stray current has the moderate impact on the corrosion of mid-slope protection net. Comprehensive evaluation on the corrosive degree of soil samples indicates that the corrosion of upper slope is moderate, and the corrosion of mid-slope and lower slope is strong. Organic matter in soil is remarkably relevant to electric potential gradient. Available nitrogen, available potassium and available phosphorus are remarkably relevant to anions. The distribution of soil nutrient is indirectly relevant to slope type.

  12. Impact of Soil Composition and Electrochemistry on Corrosion of Rock-cut Slope Nets along Railway Lines in China

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    Taking the slope of Suiyu Railway to study, the research separately studied soil resistivity, soil electrochemistry (corrosion potential, oxidization reduction potential, electric potential gradient and pH), soil anions (total soluble salt, Cl-, SO42- and ), and soil nutrition (moisture content, organic matter, total nitrogen, alkali-hydrolysable nitrogen, available phosphorus, and available potassium) at different slope levels, and conducted corrosion grade evaluation on artificial soil according to its single index and comprehensive indexes. Compared with other factors, water has the biggest impact on the corrosion of slope protection net, followed by anion content. Total soluble salt has the moderate impact on the corrosion of slope protection net, and stray current has the moderate impact on the corrosion of mid-slope protection net. Comprehensive evaluation on the corrosive degree of soil samples indicates that the corrosion of upper slope is moderate, and the corrosion of mid-slope and lower slope is strong. Organic matter in soil is remarkably relevant to electric potential gradient. Available nitrogen, available potassium and available phosphorus are remarkably relevant to anions. The distribution of soil nutrient is indirectly relevant to slope type.

  13. Surface analysis and electrochemistry of a robust carbon-nanofiber-based electrode platform H2O2 sensor

    NASA Astrophysics Data System (ADS)

    Suazo-Dávila, D.; Rivera-Meléndez, J.; Koehne, J.; Meyyappan, M.; Cabrera, C. R.

    2016-10-01

    A vertically aligned carbon nanofiber-based (VACNF) electrode platform was developed for an enzymeless hydrogen peroxide sensor. Vertical nanofibers have heights on the order of 2-3 μm, and diameters that vary from 50 to 100 nm as seen by atomic force microscopy. The VACNF was grown as individual, vertically, and freestanding structures using plasma-enhanced chemical vapor deposition. The electrochemical sensor, for the hydrogen peroxide measurement in solution, showed stability and reproducibility in five consecutive calibration curves with different hydrogen peroxide concentrations over a period of 3 days. The detection limit was 66 μM. The sensitivity for hydrogen peroxide electrochemical detection was 0.0906 mA cm-2 mM-1, respectively. The sensor was also used for the measurement of hydrogen peroxide as the by-product of the reaction of cholesterol with cholesterol oxidase as a biosensor application. The sensor exhibits linear behavior in the range of 50 μM-1 mM in cholesterol concentrations. The surface analysis and electrochemistry characterization is presented.

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

    PubMed

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

    2016-05-15

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

  15. Electrochemistry at nanoscale electrodes: individual single-walled carbon nanotubes (SWNTs) and SWNT-templated metal nanowires.

    PubMed

    Dudin, Petr V; Snowden, Michael E; Macpherson, Julie V; Unwin, Patrick R

    2011-12-27

    Individual nanowires (NWs) and native single-walled carbon nanotubes (SWNTs) can be readily used as well-defined nanoscale electrodes (NSEs) for voltammetric analysis. Here, the simple photolithography-free fabrication of submillimeter long Au, Pt, and Pd NWs, with sub-100 nm heights, by templated electrodeposition onto ultralong flow-aligned SWNTs is demonstrated. Both individual Au NWs and SWNTs are employed as NSEs for electron-transfer (ET) kinetic quantification, using cyclic voltammetry (CV), in conjunction with a microcapillary-based electrochemical method. A small capillary with internal diameter in the range 30-70 μm, filled with solution containing a redox-active mediator (FcTMA(+) ((trimethylammonium)methylferrocene), Fe(CN)(6)(4-), or hydrazine) is positioned above the NSE, so that the solution meniscus completes an electrochemical cell. A 3D finite-element model, faithfully reproducing the experimental geometry, is used to both analyze the experimental CVs and derive the rate of heterogeneous ET, using Butler-Volmer kinetics. For a 70 nm height Au NW, intrinsic rate constants, k(0), up to ca. 1 cm s(-1) can be resolved. Using the same experimental configuration the electrochemistry of individual SWNTs can also be accessed. For FcTMA(+/2+) electrolysis the simulated ET kinetic parameters yield very fast ET kinetics (k(0) > 2 ± 1 cm s(-1)). Some deviation between the experimental voltammetry and the idealized model is noted, suggesting that double-layer effects may influence ET at the nanoscale.

  16. Impact of Soil Composition and Electrochemistry on Corrosion of Rock-cut Slope Nets along Railway Lines in China

    PubMed Central

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

    2015-01-01

    Taking the slope of Suiyu Railway to study, the research separately studied soil resistivity, soil electrochemistry (corrosion potential, oxidization reduction potential, electric potential gradient and pH), soil anions (total soluble salt, Cl−, SO42− and ), and soil nutrition (moisture content, organic matter, total nitrogen, alkali-hydrolysable nitrogen, available phosphorus, and available potassium) at different slope levels, and conducted corrosion grade evaluation on artificial soil according to its single index and comprehensive indexes. Compared with other factors, water has the biggest impact on the corrosion of slope protection net, followed by anion content. Total soluble salt has the moderate impact on the corrosion of slope protection net, and stray current has the moderate impact on the corrosion of mid-slope protection net. Comprehensive evaluation on the corrosive degree of soil samples indicates that the corrosion of upper slope is moderate, and the corrosion of mid-slope and lower slope is strong. Organic matter in soil is remarkably relevant to electric potential gradient. Available nitrogen, available potassium and available phosphorus are remarkably relevant to anions. The distribution of soil nutrient is indirectly relevant to slope type. PMID:26450811

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

    PubMed

    Ozkan, Sibel A; Uslu, Bengi

    2016-10-25

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

  18. Effect of alpha-cyclodextrin on drug distribution studied by electrochemistry at interfaces between immiscible electrolyte solutions.

    PubMed

    Deryabina, Maria A; Hansen, Steen H; Østergaard, Jesper; Jensen, Henrik

    2009-05-21

    The description and understanding of noncovalent interactions and distribution of potential new drug compounds in an organism is of paramount importance for the successful development of new drugs. In this work, a new procedure based on electrochemistry at the interface between two immiscible electrolyte solutions (ITIES) for addressing and discriminating between drug compound/ligand interactions in aqueous solution and nonspecific ligand effects on oil-water distribution behavior has been developed. The procedure is demonstrated using five drug compounds with different physical chemical parameters and alpha-cyclodextrin as the aqueous phase ligand. Alpha-cyclodextrin was chosen as an aqueous phase ligand, as it is frequently used in drug formulations to enhance solubility and bioavailability of drug compounds. Supplementary capillary electrophoresis experiments provided more detailed information on alpha-cyclodextrin drug complexation and, in combination with the electrochemical studies, provided information on solvation effects affecting the oil-water distribution of the drug compounds. The use of ligand shift ion partition diagrams for data presentation is a convenient format for the visualization of ligand effects on distribution behavior of related drug compounds.

  19. Teaching Physiology and the World Wide Web: Electrochemistry and Electrophysiology on the Internet.

    ERIC Educational Resources Information Center

    Dwyer, Terry M.; Fleming, John; Randall, James E.; Coleman, Thomas G.

    1997-01-01

    Presents two examples of laboratory exercises using the World Wide Web for first-year medical students. The first example introduces the physical laws that apply to osmotic, chemical, and electrical gradients and a simulation of the ability of the sodium-potassium pump to establish chemical gradients and maintain cell volume. The second module…

  20. The Quartz Crystal Microbalance as an In Situ Tool in Electrochemistry

    DTIC Science & Technology

    1989-06-29

    were the first to study monolayer deposits on the QCM. They produced underpotential deposits (UPD) of silver on the QCM and made ex situ mass...of the EQCM to Electrochemical Systems Underpotential Deposits Bruckenstein and Swathirajan were the first to apply the QCM to the measurement of...masses of underpotential deposits (18), providing direct mass measurements of Ag and Pb UPD monolayers on Au electrodes. As pointed out above, these were

  1. Synthesis, photophysics, electrochemistry, thermal stability and electroluminescent performances of a new europium complex with bis(β-diketone) ligand containing carbazole group.

    PubMed

    Liu, Jian; Liang, Quan-Bin; Wu, Hong-Bin

    2016-09-07

    We synthesized a new europium complex [Eu(ecbpd)3 (Phen)] with bis(β-diketone) ligand containing a carbazole group, in which ecbpd and Phen are dehydro-3,3'-(9-ethyl-9H-carbazole-3,6-diyl)bis(1-phenylpropane-1,3-dione) and 1,10-phenanthroline, respectively. Its UV/vis and photoluminescent spectra, quantum yield, luminescence lifetime, electrochemistry, thermal stability and electroluminescent performances were studied. This europium complex showed low efficiency luminescence, which is probably due to the mismatching energy levels of its ligand and Eu(3)(+) , as well as the double Eu(3)(+) core resonance.

  2. Modeling of Pressurized Electrochemistry and Steam-Methane Reforming in Solid Oxide Fuel Cells and the Effects on Thermal and Electrical Stack Performance

    SciTech Connect

    Recknagle, Kurtis P.; Khaleel, Mohammad A.

    2009-03-01

    Summarizes work done to extend the electrochemical performance and methane reforming submodels to include the effects of pressurization and to demonstrate this new modeling capability by simulating large stacks operating on methane-rich fuel under pressurized and non-pressurized conditions. Pressurized operation boosts electrochemical performance, alters the kinetics of methane reforming, and effects the equilibrium composition of methane fuels. This work developed constitutive submodels that couple the electrochemistry, reforming, and pressurization to yield an increased capability of the modeling tool for prediction of SOFC stack performance.

  3. Insight in layer-by-layer assembly of cysteamine and L-cysteine on the copper surface by electrochemistry and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Song, Ping; Shen, Shu; Li, Chuan-Chuan; Guo, Xiao-Yu; Wen, Ying; Yang, Hai-Feng

    2015-02-01

    In this work, we examined the relationship between the anticorrosion behavior and the structure of the cysteamine/L-cysteine layer-by-layer coating on the copper surface via the self-assembled monolayers (SAMs) technique with electrochemistry and surface-enhanced Raman scattering (SERS) spectroscopy. SERS results elucidated the layer-by-layer adsorption mechanism of cysteamine/L-cysteine at the copper surface. Electrochemical investigations explored the inhibition behavior of cysteamine/L-cysteine for copper from corrosion with a high protection efficiency of 91.4%.

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

    PubMed

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

    2015-02-07

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

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

    NASA Astrophysics Data System (ADS)

    Gupta, Sanju; Irihamye, Aline

    2015-03-01

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

  6. Fully solar-driven thermo- and electrochemistry for advanced oxidation processes (STEP-AOPs) of 2-nitrophenol wastewater.

    PubMed

    Nie, Chunhong; Shao, Nan; Wang, Baohui; Yuan, Dandan; Sui, Xin; Wu, Hongjun

    2016-07-01

    The STEP (Solar Thermal Electrochemical Process) for Advanced Oxidation Processes (AOPs, combined to STEP-AOPs), fully driven by solar energy without the input of any other forms of energy and chemicals, is introduced and demonstrated from the theory to experiments. Exemplified by the persistent organic pollutant 2-nitrophenol in water, the fundamental model and practical system are exhibited for the STEP-AOPs to efficiently transform 2-nitrophenol into carbon dioxide, water, and the other substances. The results show that the STEP-AOPs system performs more effectively than classical AOPs in terms of the thermodynamics and kinetics of pollutant oxidation. Due to the combination of solar thermochemical reactions with electrochemistry, the STEP-AOPs system allows the requisite electrolysis voltage of 2-nitrophenol to be experimentally decreased from 1.00 V to 0.84 V, and the response current increases from 18 mA to 40 mA. STEP-AOPs also greatly improve the kinetics of the oxidation at 30 °C and 80 °C. As a result, the removal rate of 2-nitrophenol after 1 h increased from 19.50% at 30 °C to 32.70% at 80 °C at constant 1.90 V. Mechanistic analysis reveals that the oxidation pathway is favorably changed because of thermal effects. The tracking of the reaction displayed that benzenediol and hydroquinone are initial products, with maleic acid and formic acid as sequential carboxylic acid products, and carbon dioxide as the final product. The theory and experiments on STEP-AOPs system exemplified by the oxidation of 2-nitrophenol provide a broad basis for extension of the STEP and AOPs for rapid and efficient treatment of organic wastewater.

  7. A multi-site array for combined local electrochemistry and electrophysiology in the non-human primate brain

    PubMed Central

    Disney, Anita A; McKinney, Collin; Grissom, Larry; Lu, Xuekun; Reynolds, John H

    2015-01-01

    Background Currently, the primary technique employed in circuit-level study of the brain is electrophysiology, recording local field or action potentials (LFPs or APs). However most communication between neurons is chemical and the relationship between electrical activity within neurons and chemical signaling between them is not well understood in vivo, particularly for molecules that signal at least in part by non-synaptic transmission. New Method We describe a multi-contact array and accompanying head stage circuit that together enable concurrent electrophysiological and electrochemical recording. The array is small (<200μm) and can be assembled into a device of arbitrary length. It is therefore well-suited for use in all major in vivo model systems in neuroscience, including non-human primates where the large brain and need for daily insertion and removal of recording devices places particularly strict demands on design. Results We present a protocol for array fabrication. We then show that a device built in the manner described can record LFPs and perform enzyme-based amperometric detection of choline in the awake macaque monkey. Comparison with existing methods Existing methods allow single mode (electrophysiology or electrochemistry) recording. This system is designed for concurrent, dual-mode recording. It is also the only system designed explicitly to meet the challenges of recording in non-human primates. Conclusions Our system offers the possibility for conducting in vivo studies in a range of species that examine the relationship between the electrical activity of neurons and their chemical environment, with exquisite spatial and temporal precision. PMID:26226654

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

    PubMed

    Sheng, Qinglin; Liu, Ruixiao; Zheng, Jianbin

    2013-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  10. In situ solid-state electrochemistry of mass-selected ions at well-defined electrode-electrolyte interfaces.

    PubMed

    Prabhakaran, Venkateshkumar; Johnson, Grant E; Wang, Bingbing; Laskin, Julia

    2016-11-22

    Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEIs) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and application of solid-state in situ thin-film electrochemical cells to explore redox and catalytic processes occurring at well-defined EEIs generated using soft-landing (SL) of mass- and charge-selected cluster ions. In situ cells with excellent mass-transfer properties are fabricated using carefully designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy. SL is, therefore, demonstrated to be a unique tool for studying fundamental processes occurring at EEIs. Using an aprotic cell, the effect of charge state ([Formula: see text]) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEIs with POM anions generated by electrospray ionization and gas-phase dissociation. Additionally, a proton-conducting cell has been developed to characterize the oxygen reduction activity of bare Pt clusters (Pt30 ∼1 nm diameter), thus demonstrating the capability of the cell for probing catalytic reactions in controlled gaseous environments. By combining the developed in situ electrochemical cell with ion SL we established a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely defined conditions. This capability will advance the molecular-level understanding of processes occurring at EEIs that are critical to many energy-related technologies.

  11. Probing Protein 3D Structures and Conformational Changes Using Electrochemistry-Assisted Isotope Labeling Cross-Linking Mass Spectrometry.

    PubMed

    Zheng, Qiuling; Zhang, Hao; Wu, Shiyong; Chen, Hao

    2016-05-01

    This study presents a new chemical cross-linking mass spectrometry (MS) method in combination with electrochemistry and isotope labeling strategy for probing both protein three-dimensional (3D) structures and conformational changes. For the former purpose, the target protein/protein complex is cross-linked with equal mole of premixed light and heavy isotope labeled cross-linkers carrying electrochemically reducible disulfide bonds (i.e., DSP-d0 and DSP-d8 in this study, DSP = dithiobis[succinimidyl propionate]), digested and then electrochemically reduced followed with online MS analysis. Cross-links can be quickly identified because of their reduced intensities upon electrolysis and the presence of doublet isotopic peak characteristics. In addition, electroreduction converts cross-links into linear peptides, facilitating MS/MS analysis to gain increased information about their sequences and modification sites. For the latter purpose of probing protein conformational changes, an altered procedure is adopted, in which the protein in two different conformations is cross-linked using DSP-d0 and DSP-d8 separately, and then the two protein samples are mixed in 1:1 molar ratio. The merged sample is subjected to digestion and electrochemical mass spectrometric analysis. In such a comparative cross-linking experiment, cross-links could still be rapidly recognized based on their responses to electrolysis. More importantly, the ion intensity ratios of light and heavy isotope labeled cross-links reveal the conformational changes of the protein, as exemplified by examining the effect of Ca(2+) on calmodulin conformation alternation. This new cross-linking MS method is fast and would have high value in structural biology. Graphical Abstract ᅟ.

  12. Probing Protein 3D Structures and Conformational Changes Using Electrochemistry-Assisted Isotope Labeling Cross-Linking Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zheng, Qiuling; Zhang, Hao; Wu, Shiyong; Chen, Hao

    2016-05-01

    This study presents a new chemical cross-linking mass spectrometry (MS) method in combination with electrochemistry and isotope labeling strategy for probing both protein three-dimensional (3D) structures and conformational changes. For the former purpose, the target protein/protein complex is cross-linked with equal mole of premixed light and heavy isotope labeled cross-linkers carrying electrochemically reducible disulfide bonds (i.e., DSP-d0 and DSP-d8 in this study, DSP = dithiobis[succinimidyl propionate]), digested and then electrochemically reduced followed with online MS analysis. Cross-links can be quickly identified because of their reduced intensities upon electrolysis and the presence of doublet isotopic peak characteristics. In addition, electroreduction converts cross-links into linear peptides, facilitating MS/MS analysis to gain increased information about their sequences and modification sites. For the latter purpose of probing protein conformational changes, an altered procedure is adopted, in which the protein in two different conformations is cross-linked using DSP-d0 and DSP-d8 separately, and then the two protein samples are mixed in 1:1 molar ratio. The merged sample is subjected to digestion and electrochemical mass spectrometric analysis. In such a comparative cross-linking experiment, cross-links could still be rapidly recognized based on their responses to electrolysis. More importantly, the ion intensity ratios of light and heavy isotope labeled cross-links reveal the conformational changes of the protein, as exemplified by examining the effect of Ca2+ on calmodulin conformation alternation. This new cross-linking MS method is fast and would have high value in structural biology.

  13. A quantitative assay for reductive metabolism of a pesticide in fish using electrochemistry coupled with liquid chromatography tandem mass spectrometry.

    PubMed

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

    2015-04-07

    This is the first study to use electrochemistry to generate a nitro reduction metabolite as a standard for a liquid chromatography-mass spectrometry-based quantitative assay. This approach is further used to quantify 3-trifluoromethyl-4-nitrophenol (TFM) reductive metabolism. TFM is a widely used pesticide for the population control of sea lamprey (Petromyzon marinus), an invasive species of the Laurentian Great Lakes. Three animal models, sea lamprey, lake sturgeon (Acipenser fulvescens), and rainbow trout (Oncorhynchus mykiss), were selected to evaluate TFM reductive metabolism because they have been known to show differential susceptibilities to TFM toxicity. Amino-TFM (aTFM; 3-trifluoromethyl-4-aminophenol) was the only reductive metabolite identified through liquid chromatography-high-resolution mass spectrometry screening of liver extracts incubated with TFM and was targeted for electrochemical synthesis. After synthesis and purification, aTFM was used to develop a quantitative assay of the reductive metabolism of TFM through liquid chromatography and tandem mass spectrometry. The concentrations of aTFM were measured from TFM-treated cellular fractions, including cytosolic, nuclear, membrane, and mitochondrial protein extracts. Sea lamprey extracts produced the highest concentrations (500 ng/mL) of aTFM. In addition, sea lamprey and sturgeon cytosolic extracts showed concentrations of aTFM substantially higher than those of rainbow trout. However, other fractions of lake sturgeon extracts tend to show aTFM concentrations similar to those of rainbow trout but not with sea lamprey. These data suggest that the level of reductive metabolism of TFM may be associated with the sensitivities of the animals to this particular pesticide.

  14. Electrochemistry and analytical determination of lysergic acid diethylamide (LSD) via adsorptive stripping voltammetry.

    PubMed

    Merli, Daniele; Zamboni, Daniele; Protti, Stefano; Pesavento, Maria; Profumo, Antonella

    2014-12-01

    Lysergic acid diethylamide (LSD) is hardly detectable and quantifiable in biological samples because of its low active dose. Although several analytical tests are available, routine analysis of this drug is rarely performed. In this article, we report a simple and accurate method for the determination of LSD, based on adsorptive stripping voltammetry in DMF/tetrabutylammonium perchlorate, with a linear range of 1-90 ng L(-1) for deposition times of 50s. LOD of 1.4 ng L(-1) and LOQ of 4.3 ng L(-1) were found. The method can be also applied to biological samples after a simple extraction with 1-chlorobutane.

  15. Vibrational properties of fractionally charged molecules and their relevance for molecular electronics and electrochemistry

    NASA Astrophysics Data System (ADS)

    Bâldea, Ioan

    2017-01-01

    Important insight into the charge transfer across interfaces can be gained in situations wherein, for given adsorbate and substrate species, the (fractional) charge state of the adsorbed molecules can be varied in a controlled way. Applied biases can continuously tune the charge of molecules embedded in nanojunctions and/or in electrochemical setups but information on the fractional charges of the corresponding partial oxidized/reduced states cannot be directly accessed in experiments. Here, we present theoretical results revealing that information on the fractional molecular charge can be obtained by monitoring molecular vibrational properties, which can be measured by means of surface enhanced Raman spectroscopy (SERS). To this aim, we performed DFT calculations for the benchmark 1,4-benzenedithiol molecule. The changes in the vibrational frequencies are considerably larger than those recently measured in combined transport-SERS studies on molecular junctions based on fullerene. We believe that this theoretical result is an encouraging message to experimentalists.

  16. Direct electrochemistry of Shewanella loihica PV-4 on gold nanoparticles-modified boron-doped diamond electrodes fabricated by layer-by-layer technique.

    PubMed

    Wu, Wenguo; Xie, Ronggang; Bai, Linling; Tang, Zuming; Gu, Zhongze

    2012-05-01

    Microbial Fuel Cells (MFCs) are robust devices capable of taping biological energy, converting pollutants into electricity through renewable biomass. The fabrication of nanostructured electrodes with good bio- and electrochemical activity, play a profound role in promoting power generation of MFCs. Au nanoparticles (AuNPs)-modified Boron-Doped Diamond (BDD) electrodes are fabricated by layer-by-layer (LBL) self-assembly technique and used for the direct electrochemistry of Shewanella loihica PV-4 in an electrochemical cell. Experimental results show that the peak current densities generated on the Au/PAH multilayer-modified BDD electrodes increased from 1.25 to 2.93 microA/cm(-2) as the layer increased from 0 to 6. Different cell morphologies of S. loihica PV-4 were also observed on the electrodes and the highest density of cells was attached on the (Au/PAH)6/BDD electrode with well-formed three-dimensional nanostructure. The electrochemistry of S. loihica PV-4 was enhanced on the (Au/PAH)4/BDD electrode due to the appropriate amount of AuNPsand thickness of PAH layer.

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

    PubMed

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

    2009-02-01

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

  18. Surfaces of action: cells and membranes in electrochemistry and the life sciences.

    PubMed

    Grote, Mathias

    2010-09-01

    The term 'cell', in addition to designating fundamental units of life, has also been applied since the nineteenth century to technical apparatuses such as fuel and galvanic cells. This paper shows that such technologies, based on the electrical effects of chemical reactions taking place in containers, had a far-reaching impact on the concept of the biological cell. My argument revolves around the controversy over oxidative phosphorylation in bioenergetics between 1961 and 1977. In this scientific conflict, a two-level mingling of technological culture, physical chemistry and biological research can be observed. First, Peter Mitchell explained the chemiosmotic hypothesis of energy generation by representing cellular membrane processes via an analogy to fuel cells. Second, in the associated experimental scrutiny of membranes, material cell models were devised that reassembled spatialized molecular processes in vitro. Cells were thus modelled both on paper and in the test tube not as morphological structures but as compartments able to perform physicochemical work. The story of cells and membranes in bioenergetics points out the role that theories and practices in physical chemistry had in the molecularization of life. These approaches model the cell as a 'topology of molecular action', as I will call it, and it involves concepts of spaces, surfaces and movements. They epitomize an engineer's vision of the organism that has influenced diverse fields in today's life sciences.

  19. Atomic-scale electrochemistry on the surface of a manganite by scanning tunneling microscopy

    SciTech Connect

    Vasudevan, Rama K. Tselev, Alexander; Baddorf, Arthur P.; Gianfrancesco, Anthony G.

    2015-04-06

    The doped manganese oxides (manganites) have been widely studied for their colossal magnetoresistive effects, for potential applications in oxide spintronics, electroforming in resistive switching devices, and are materials of choice as cathodes in modern solid oxide fuel cells. However, little experimental knowledge of the dynamics of the surfaces of perovskite manganites at the atomic scale exists. Here, through in-situ scanning tunneling microscopy (STM), we demonstrate atomic resolution on samples of La{sub 0.625}Ca{sub 0.375}MnO{sub 3} grown on (001) SrTiO{sub 3} by pulsed laser deposition. Furthermore, by applying triangular DC waveforms of increasing amplitude to the STM tip, and measuring the tunneling current, we demonstrate the ability to both perform and monitor surface electrochemical processes at the atomic level, including formation of oxygen vacancies and removal and deposition of individual atomic units or clusters. Our work paves the way for better understanding of surface oxygen reactions in these systems.

  20. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

    DOE PAGES

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

    2017-03-16

    First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solvemore » the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Lastly, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.« less

  1. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solve the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Finally, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.

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

    PubMed

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

    2010-09-17

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

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

    PubMed

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

    2017-05-01

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

  4. Redox-dependent spatially resolved electrochemistry at graphene and graphite step edges.

    PubMed

    Güell, Aleix G; Cuharuc, Anatolii S; Kim, Yang-Rae; Zhang, Guohui; Tan, Sze-yin; Ebejer, Neil; Unwin, Patrick R

    2015-04-28

    The electrochemical (EC) behavior of mechanically exfoliated graphene and highly oriented pyrolytic graphite (HOPG) is studied at high spatial resolution in aqueous solutions using Ru(NH3)6(3+/2+) as a redox probe whose standard potential sits close to the intrinsic Fermi level of graphene and graphite. When scanning electrochemical cell microscopy (SECCM) data are coupled with that from complementary techniques (AFM, micro-Raman) applied to the same sample area, different time-dependent EC activity between the basal planes and step edges is revealed. In contrast, other redox couples (ferrocene derivatives) whose potential is further removed from the intrinsic Fermi level of graphene and graphite show uniform and high activity (close to diffusion-control). Macroscopic voltammetric measurements in different environments reveal that the time-dependent behavior after HOPG cleavage, peculiar to Ru(NH3)6(3+/2+), is not associated particularly with any surface contaminants but is reasonably attributed to the spontaneous delamination of the HOPG with time to create partially coupled graphene layers, further supported by conductive AFM measurements. This process has a major impact on the density of states of graphene and graphite edges, particularly at the intrinsic Fermi level to which Ru(NH3)6(3+/2+) is most sensitive. Through the use of an improved voltammetric mode of SECCM, we produce movies of potential-resolved and spatially resolved HOPG activity, revealing how enhanced activity at step edges is a subtle effect for Ru(NH3)6(3+/2+). These latter studies allow us to propose a microscopic model to interpret the EC response of graphene (basal plane and edges) and aged HOPG considering the nontrivial electronic band structure.

  5. Single-Molecule Electrochemistry on a Porous Silica-Coated Electrode.

    PubMed

    Lu, Jin; Fan, Yunshan; Howard, Marco D; Vaughan, Joshua C; Zhang, Bo

    2017-03-01

    Here we report the direct observation and quantitative analysis of single redox events on a modified indium-tin oxide (ITO) electrode. The key in the observation of single redox events are the use of a fluorogenic redox species and the nanoconfinement and hindered redox diffusion inside 3-nm-diameter silica nanochannels. A simple electrochemical process was used to grow an ultrathin silica film (∼100 nm) consisting of highly ordered parallel nanochannels exposing the electrode surface from the bottom. The electrode-supported 3-nm-diameter nanochannels temporally trap fluorescent resorufin molecules resulting in hindered molecular diffusion in the vicinity of the electrode surface. Adsorption, desorption, and heterogeneous redox events of individual resorufin molecules can be studied using total-internal reflection fluorescence (TIRF). The rate constants of adsorption and desorption processes of resorufin were characterized from single-molecule analysis to be (1.73 ± 0.08) × 10(-4) cm·s(-1) and 15.71 ± 0.76 s(-1), respectively. The redox events of resorufin to the non-fluorescent dihydroresorufin were investigated by analyzing the change in surface population of single resorufin molecules with applied potential. The scan-rate-dependent molecular counting results (single-molecule fluorescence voltammetry) indicated a surface-controlled electrochemical kinetics of the resorufin reduction on the modified ITO electrode. This study demonstrates the great potential of mesoporous silica as a useful modification scheme for studying single redox events on a variety of transparent substrates such as ITO electrodes and gold or carbon film coated glass electrodes. The ability to electrochemically grow and transfer mesoporous silica films onto other substrates makes them an attractive material for future studies in spatial heterogeneity of electrocatalytic surfaces.

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

    SciTech Connect

    Gupta, Sanju; Irihamye, Aline

    2015-03-15

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

  7. The Hydrothermal Synthesis and Electrochemistry of Oxyfluorides and Fluoro-bronzes for Lithium and Multivalent Battery Cathodes

    NASA Astrophysics Data System (ADS)

    Incorvati, Jared T.

    experiments on the electrochemistry of organic materials, a new phenomenon in contact electrification is described wherein insulators charge with one polarity before becoming uncharged then finally charging with the opposite polarity. The likelihood of contact charging insulators to undergo polarity reversal is linked to the difference in the materials' Young's moduli. X-ray photoelectron spectroscopy, atomic force microscopy, and Kelvin force microscopy surface studies reveal that exchanged materials act as charge carriers in these systems.

  8. In-Situ TEM Electrochemistry of Individual Nanowire and Nanoparticle Electrodes in a Li-Ion Cell

    NASA Astrophysics Data System (ADS)

    Huang, Jianyu

    2012-02-01

    Recently, we created the first Li-ion electrochemical cell inside a transmission electron microscope (TEM) and observed, in real time with atomic scale resolution, the lithiation/delithiation processes. This experiment opened the door for a suite of experimental studies involving in-situ TEM characterization of Li-ion battery materials. In this presentation, I'll first review our latest progress of using the in-situ electrochemical cell setup inside the TEM to reveal the intrinsic electrochemistry of several high energy density anode materials such as SnO2, ZnO, Si, Ge, Al nanowires, Si nanoparticles, carbon nanotubes, and graphene. Several electrochemical mechanisms were observed and characterized in real-time, including lithiation induced stress, volume changes, phase transformations, pulverization, cracking, embrittlement, and mechanical failure in anode materials. These results indicate the strong material, size and crystallographic orientation dependent electrochemical behavior and degradation mechanisms that occur in Li-ion battery anodes. In the future, we will need further advancements in in-situ characterization for understanding important processes in Li-ion batteries. For example, liquid cells are required in order to examine the electrochemical reactions between battery materials and the standard battery electrolytes, which are ethylene carbonate-based. Furthermore, in-situ studies need to be correlated with electrochemical studies performed on bulk electrodes. I will present a comparison between our in-situ results and electrochemical studies on conventional battery electrodes and highlight how in-situ studies can have important impact on the design of Li-ion batteries. Finally I will discuss outstanding challenging issues and opportunities in the field of Li-ion battery research. [4pt] References: Science 330, 1515 (2010); 330, 1485 (2010); Nano Lett. Doi: 10.1021/nl200412p, 10.1021/nl2024118, 10.1021/nl201684d, 10.1021/nl202088h, ACS Nano, doi: 10

  9. Analysis of Various Bibliometric Indicators for the Evaluation of Scientific Journals and Scientists

    NASA Astrophysics Data System (ADS)

    Guz, A. N.; Rushchitsky, J. J.

    2013-05-01

    Features of applying bibliometric indicators for scientific journals and scientists are discussed using, as examples, scientists of the S. P. Timoshenko Institute of Mechanics and the journal Prikladnaya Mekhanika ( International Applied Mechanics), which is published by the institute in Russian and by Springer in English. Old and new scientific databases are described and commented on. Consideration is given to citation as the most popular parameter for bibliometric indicators, the Hirsch and Egghe indices as criteria for the evaluation of scientists, the Hirsch index, Impact-Factor, SJR, SNIP, and RIP as criteria for the evaluation of scientific journals, and a new approach to evaluation based on full-text article requests. In 1991-2011, Prikladnaya Mekhanika ( International Applied Mechanics) had highest indicators among all Ukrainian scientific journals: Impact-Factor = 1.740 in 2005, SJR = 0.240 in 2006, RIP = 1.76 in 2006, SNIP = 2.45 in 2011

  10. End-of-Discharge and End-of-Life Prediction in Lithium-Ion Batteries with Electrochemistry-Based Aging Models

    NASA Technical Reports Server (NTRS)

    Daigle, Matthew; Kulkarni, Chetan S.

    2016-01-01

    As batteries become increasingly prevalent in complex systems such as aircraft and electric cars, monitoring and predicting battery state of charge and state of health becomes critical. In order to accurately predict the remaining battery power to support system operations for informed operational decision-making, age-dependent changes in dynamics must be accounted for. Using an electrochemistry-based model, we investigate how key parameters of the battery change as aging occurs, and develop models to describe aging through these key parameters. Using these models, we demonstrate how we can (i) accurately predict end-of-discharge for aged batteries, and (ii) predict the end-of-life of a battery as a function of anticipated usage. The approach is validated through an experimental set of randomized discharge profiles.

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

    PubMed

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

    2013-07-22

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

  12. Type I collagen-mediated synthesis of noble metallic nanoparticles networks and the applications in Surface-Enhanced Raman Scattering and electrochemistry.

    PubMed

    Sun, Yujing; Sun, Lanlan; Zhang, Baohua; Xu, Fugang; Liu, Zhelin; Guo, Cunlan; Zhang, Yue; Li, Zhuang

    2009-08-15

    In this paper, we demonstrated an effective environmentally friendly synthesis route to prepare noble metallic (Au, Ag, Pt and Pd) nanoparticles (NPs) networks mediated by type I collagen in the absence of any seeds or surfactants. In the reactions, type I collagen served as stabilizing agent and assembly template for the synthesized metallic NPs. The hydrophobic interaction between collagen and mica interface as well as the hydrogen bonds between inter- and intra-collagen molecules play important roles in the formation of collagen-metallic NPs networks. The noble metallic NPs networks have many advantages in the applications of Surface-Enhanced Raman Scattering (SERS) and electrochemistry detection. Typically, the as-prepared Ag NPs networks reveal great Raman enhancement activity for 4-ATP, and can even be used to detect low concentration of DNA base, adenine, without any label step. Furthermore, the cyclic voltammograms showed Pt NPs networks have good electrocatalytic ability for the reduction of O(2).

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

    PubMed

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

    2015-07-15

    We demonstrate a flexible combined electrochemistry and fiber optics-based in situ UV/vis spectroscopy setup to gain insight into the depth evolution of electrochemical hydride and oxide formation in Pd films with thicknesses of 20 and 100 nm. The thicknesses of our model systems are chosen such that the films are thinner or significantly thicker than the optical skin depth of Pd to create two distinctly different situations. Low power white light is irradiated on the sample and analyzed in three different configurations; transmittance through, and, reflectance from the front and the back side of the film. The obtained optical sensitivities correspond to fractions of a monolayer of adsorbed or absorbed hydrogen (H) and oxygen (O) on Pd. Moreover, a combined simultaneous readout obtained from the different optical measurement configurations provides mechanistic insights into the depth-evolution of the studied hydrogenation and oxidation processes.

  14. Li/Ag2VO2PO4 batteries: the roles of composite electrode constituents on electrochemistry

    SciTech Connect

    Bock, David C.; Bruck, Andrea M.; Pelliccione, Christopher J.; Zhang, Yiman; Takeuchi, Kenneth J.; Marschilok, Amy C.; Takeuchi, Esther S.

    2016-11-01

    In this study, we utilize silver vanadium phosphorous oxide, Ag2VO2PO4, as a model system to systematically study the impact of the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Notably, although highly resistive, this bimetallic cathode can be discharged as a pure electroactive material in the absence of a conductive additive as it generates an in situ conductive matrix via a reduction displacement reaction resulting in the formation of silver metal nanoparticles. Also, three different electrode compositions were investigated: Ag2VO2PO4 only, Ag2VO2PO44 with binder, and Ag2VO2PO4 with binder and carbon. Constant current discharge, pulse testing and impedance spectroscopy measurements were used to characterize the electrochemical properties of the electrodes as a function of depth of discharge. In situ EDXRD was used to spatially resolve the discharge progression within the cathode by following the formation of Ag0. Ex situ XRD and EXAFS modeling were used to quantify the amount of Ag0 formed. Results indicate that the metal center reduced (V5+ or Ag+) was highly dependent on composite composition (presence of PTFE, carbon), depth of discharge (Ag0 nanoparticle formation), and spatial location within the cathode. The addition of a binder was found to increase cell polarization, and the percolation network provided by the carbon in the presence of PTFE was further increased with reduction and formation of Ag0. Lastly, this study provides insight into the factors controlling the electrochemistry of resistive active materials in composite electrodes.

  15. Modern aspects of electrochemistry

    SciTech Connect

    Bockris, J.M.; Conway, B.E.; White, R.E.

    1986-01-01

    This book presents information on the following topics: perspectives in electrochemical physics; modern state of double layer study of solid metals; photoelectrolysis and photoelectrochemical catalysis; electron transfer reactions on oxide-covered metal electrodes; and interfacial electrostatics and electrodynamics in disperse systems.

  16. Nanomaterials in Electrochemistry

    DTIC Science & Technology

    2007-11-02

    feed solution is 1 mM in KCI and 0.5 mM in the cationic dye methylene blue , and the receiver solution is 1 mM KCI, the initially-colorless receiver...have interesting optical properties (20-22). For example, suspensions of nanoscopic Au particles can be pink, purple or blue depending on the...Au Nanotube Membranes (19). The pores in a commercially available polycarbonate filtration membrane (Poretics) were used as templates to form the

  17. Surface Electrochemistry of Metals

    DTIC Science & Technology

    1993-04-30

    171.** Auger Electron Angular Distributions from Underpotentially Deposited Ag Monolayers and Films at Pt(I 11) Pretreated with Iodine. Charles A...chemical vapor deposition (RTCVD), in which the heated Si(100) surface was carbonized with propane. Auger emission angular distributions were measured

  18. Electrochemistry of Metal Surfaces

    DTIC Science & Technology

    1990-06-30

    1-butene (BTE), 1-pentene (PTE), l-hexene (HXE), 1-- octene (OCE) and l--decene (DCE). Vibrational spectra of the adsorbed layers were obtained by use...Surface Sci., 92, 617 (1980). 39. Electrochemical Hydrogenation of Ethylene at Well-Defined Pt(100) and Pt(111) Surfaces. Arthur T. Hubbard, Mark A...Surf Sci., 147, 241 (1984). 75. A Comparison of Gas Phase and Electrochemical Hydrogenation of Ethylene at ** Platinum Surfaces. Andrzej Wieckowski

  19. Electrochemistry for Energy Conversion

    NASA Astrophysics Data System (ADS)

    O'Hayre, Ryan

    2010-10-01

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

  20. Combine electrochemistry with photocatalysis

    SciTech Connect

    Vinodgopal, K.; Kamat, P.V.

    1996-04-01

    Because a substantial percentage of colorant is lost during the dyeing process, remediation efforts have largely been focused on removing these dyes from the wastewater effluents of textile mills and other industrial colorant users. Incomplete decolorization of the effluent before discharge shifts the burden of treatment downstream. In publicly owned water treatment facilities, these dyes often end up as sludges that are dewatered and eventually deposited in landfills. There is a substantial economic impetus to develop a flow reactor to be used onstream by mills to treat colorant effluent and recycle the water. The authors have developed a photocatalytic approach using semiconductors for degrading several azo dyes. They recently found that deposition of semiconductor nanoclusters on a conducting glass surface provides a convenient way to manipulate the photocatalytic reaction by electrochemical methods. The thin semiconductor particulate film can be used as a photosensitive electrode in an electrochemical cell. The paper describes electrode preparation, the photoelectrochemical properties of TiO{sub 2} and SnO{sub 2}, reaction mechanism, and composite semiconductor films.

  1. The Applied Mathematics Laboratory.

    ERIC Educational Resources Information Center

    Siegel, Martha J.

    This report describes the Applied Mathematics Laboratory (AML) operated by the Department of Mathematics at Towson State University, Maryland. AML is actually a course offered to selected undergraduates who are given the opportunity to apply their skills in investigating industrial and governmental problems. By agreement with sponsoring…

  2. Applied Physics at Strathclyde.

    ERIC Educational Resources Information Center

    Patterson, H.; Twidell, J. W.

    1979-01-01

    Outlines and describes the content of an applied physics course offered for the four year honors and the three year pass degrees. The course stresses three components: principal subjects, industrial projects, and subsidiary subjects. (GA)

  3. Compensation: How to Apply

    MedlinePlus

    ... Benefit Rates Education & Training Education & Training Home For Students Get Started Get Started Home Apply for Benefits ... make a claims decision. Learn more about VA's responsibilities for obtaining evidence to support your disability ... Directory EMAIL UPDATES Email Address Button ...

  4. Geomorphology: Pure and applied

    SciTech Connect

    Hart, M.G.

    1986-01-01

    The book summarizes the history of intellectual debate in geomorphology and describes modern developments both ''pure'' and ''applied.'' The history begins well before W.M. Davis and follows through to such debates as those concerned with the Pleistocene. Modern developments in pure geomorphology are cast in terms of chapters on form, process, materials, and methods analysis. The applied chapters concentrate on environmental hazards and resources, and their management.

  5. Applied Learning Networks (ALN)

    DTIC Science & Technology

    2007-01-01

    AFRL-IF-RS-TR-2007-7 Final Technical Report January 2007 APPLIED LEARNING NETWORKS (ALN) University of Southern California...any other person or corporation; or convey any rights or permission to manufacture, use, or sell any patented invention that may relate to them...1-0051 4. TITLE AND SUBTITLE APPLIED LEARNING NETWORKS (ALN) 5c. PROGRAM ELEMENT NUMBER 62301E 5d. PROJECT NUMBER T981 5e. TASK NUMBER US

  6. Coupled optical absorption, charge carrier separation, and surface electrochemistry in surface disordered/hydrogenated TiO2 for enhanced PEC water splitting reaction.

    PubMed

    Behara, Dilip Kumar; Ummireddi, Ashok Kumar; Aragonda, Vidyasagar; Gupta, Prashant Kumar; Pala, Raj Ganesh S; Sivakumar, Sri

    2016-03-28

    The central governing factors that influence the efficiency of photoelectrochemical (PEC) water splitting reaction are photon absorption, effective charge-carrier separation, and surface electrochemistry. Attempts to improve one of the three factors may debilitate other factors and we explore such issues in hydrogenated TiO2, wherein a significant increase in optical absorption has not resulted in a significant increase in PEC performance, which we attribute to the enhanced recombination rate due to the formation of amorphization/disorderness in the bulk during the hydrogenation process. To this end, we report a methodology to increase the charge-carrier separation with enhanced optical absorption of hydrogenated TiO2. Current methodology involves hydrogenation of non-metal (N and S) doped TiO2 which comprises (1) lowering of the band gap through shifting of the valence band via less electronegative non-metal N, S-doping, (2) lowering of the conduction band level and the band gap via formation of the Ti(3+) state and oxygen vacancies by hydrogenation, and (3) material processing to obtain a disordered surface structure which favors higher electrocatalytic (EC) activity. This design strategy yields enhanced PEC activity (%ABPE = 0.38) for the N-S co-doped TiO2 sample hydrogenated at 800 °C for 24 h over possible combinations of N-S co-doped TiO2 samples hydrogenated at 500 °C/24 h, 650 °C/24 h and 800 °C/72 h. This suggests that hydrogenation at lower temperatures does not result in much increase in optical absorption and prolonged hydrogenation results in an increase in optical absorption but a decrease in charge carrier separation by forming disorderness/oxygen vacancies in the bulk. Furthermore, the difference in double layer capacitance (C(dl)) calculated from electrochemical impedance spectroscopy (EIS) measurements of these samples reflects the change in the electrochemical surface area (ECSA) and facilitates assessing the key role of surface

  7. PSYCHOANALYSIS AS APPLIED AESTHETICS.

    PubMed

    Richmond, Stephen H

    2016-07-01

    The question of how to place psychoanalysis in relation to science has been debated since the beginning of psychoanalysis and continues to this day. The author argues that psychoanalysis is best viewed as a form of applied art (also termed applied aesthetics) in parallel to medicine as applied science. This postulate draws on a functional definition of modernity as involving the differentiation of the value spheres of science, art, and religion. The validity criteria for each of the value spheres are discussed. Freud is examined, drawing on Habermas, and seen to have erred by claiming that the psychoanalytic method is a form of science. Implications for clinical and metapsychological issues in psychoanalysis are discussed.

  8. Applied Music (Individual Study).

    ERIC Educational Resources Information Center

    Texas Education Agency, Austin.

    Background information and resources to help students in grades 9-12 in Texas pursue an individual study contract in applied music is presented. To fulfill a contract students must publicly perform from memory, with accompaniment as specified, three selections from a list of approved music for their chosen field (instrument or voice). Material…

  9. Applied Behavior Analysis

    ERIC Educational Resources Information Center

    Szapacs, Cindy

    2006-01-01

    Teaching strategies that work for typically developing children often do not work for those diagnosed with an autism spectrum disorder. However, teaching strategies that work for children with autism do work for typically developing children. In this article, the author explains how the principles and concepts of Applied Behavior Analysis can be…

  10. Signals: Applying Academic Analytics

    ERIC Educational Resources Information Center

    Arnold, Kimberly E.

    2010-01-01

    Academic analytics helps address the public's desire for institutional accountability with regard to student success, given the widespread concern over the cost of higher education and the difficult economic and budgetary conditions prevailing worldwide. Purdue University's Signals project applies the principles of analytics widely used in…

  11. Essays on Applied Microeconomics

    ERIC Educational Resources Information Center

    Mejia Mantilla, Carolina

    2013-01-01

    Each chapter of this dissertation studies a different question within the field of Applied Microeconomics. The first chapter examines the mid- and long-term effects of the 1998 Asian Crisis on the educational attainment of Indonesian children ages 6 to 18, at the time of the crisis. The effects are identified as deviations from a linear trend for…

  12. Applied Vocational Mathematics.

    ERIC Educational Resources Information Center

    South Carolina State Dept. of Education, Columbia. Office of Vocational Education.

    Developed for use in teaching a two-semester, one-unit course, this course guide is intended to aid the high school instructor in teaching mathematical problem-solving and computational skills to vocational education students. The state-adopted textbook for general mathematics III, "Applied General Mathematics" serves as the major…

  13. Applied Linguistics in Europe

    ERIC Educational Resources Information Center

    de Bot, Kees

    2004-01-01

    In this contribution developments in Applied Linguistics in Europe are linked to major social changes that have taken place over the last decades. These include: The decline of the USSR and the end of the cold war; The development of the EEC and the EU and fading of borders; The economic growth of Western Europe; Labor migration from the south to…

  14. Africa and Applied Linguistics.

    ERIC Educational Resources Information Center

    Makoni, Sinfree, Ed.; Meinhof, Ulrike H., Ed.

    2003-01-01

    This collection of articles includes: "Introducing Applied Linguistics in Africa" (Sinfree Makoni and Ulrike H. Meinhof); "Language Ideology and Politics: A Critical Appraisal of French as Second Official Language in Nigeria" (Tope Omoniyi); "The Democratisation of Indigenous Languages: The Case of Malawi" (Themba…

  15. Applied Algebra Curriculum Modules.

    ERIC Educational Resources Information Center

    Texas State Technical Coll., Marshall.

    This collection of 11 applied algebra curriculum modules can be used independently as supplemental modules for an existing algebra curriculum. They represent diverse curriculum styles that should stimulate the teacher's creativity to adapt them to other algebra concepts. The selected topics have been determined to be those most needed by students…

  16. Applied research on glucansucrases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Although glycansucrases have been known for over 70 years, they remain relatively unknown except to a small group of researchers. Practical, applied research on glycansucrases has been focused on certain key areas. The earliest of these was the development of blood plasma extenders from dextran, d...

  17. Applied Statistics with SPSS

    ERIC Educational Resources Information Center

    Huizingh, Eelko K. R. E.

    2007-01-01

    Accessibly written and easy to use, "Applied Statistics Using SPSS" is an all-in-one self-study guide to SPSS and do-it-yourself guide to statistics. What is unique about Eelko Huizingh's approach is that this book is based around the needs of undergraduate students embarking on their own research project, and its self-help style is designed to…

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

    SciTech Connect

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

    1992-08-15

    The January 2, 1992 explosion in an electrochemistry laboratory at SRI International (SRI) resulted in the death of scientist Andrew Riley, and gained some notoriety due to its association with experimental work in the controversial field of cold fusion research. Selected components of explosion debris were subjected to forensic analyses at LLNL to elucidate potential causes of, or contributing factors to, the explosion. Interrogation of the debris by LLNL encompassed nuclear, chemical, physical, and materials investigations. Nuclear studies for the determination of tritium and neutron-activation products in stainless steel and brass were negative. No evidence of signature species indicative of orthodox nuclear events was detected. The inorganic and particulate analyses were likewise negative with respect to residues of unexpected chemical species. Such target compounds included conventional explosives, accelerants, propellants, or any exceptional industrial chemicals. The GC-MS analyses of trace organic components in the explosion debris provided perhaps the most interesting results obtained at LLNL. Although no evidence of organic explosives, oxidizers, or other unusual compounds was detected, the presence of a hydrocarbon oil in the interior of the electrochemical cell was established. It is likely that its source was lubricating fluid from the machining of the metal cell components. If residues of organic oils are present during electrolysis experiments, the potential exists for an explosive reaction in the increasingly enriched oxygen atmosphere within the headspace of a metal cell.

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

    SciTech Connect

    David C. Bock; Takeuchi, Kenneth J.; Pelliccione, Christopher J.; Zhang, Wei; Wang, Jiajun; Knehr, K. W.; Wang, Jun; Wang, Feng; West, Alan C.; Marschilok, Amy C.; Takeuchi, Esther S.

    2016-04-20

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

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

    PubMed

    Shishkin, M; Ziegler, T

    2014-02-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    PubMed

    Tu, Wenwen; Lei, Jianping; Ju, Huangxian

    2009-01-01

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

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

    PubMed

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

    2009-11-15

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

  4. Quality in applied science

    NASA Astrophysics Data System (ADS)

    Sten, T.

    1993-12-01

    Science is in many senses a special kind of craft and only skilled craftsmen are able to distinguish good work from bad. Due to the variation in approaches, methods and even philosophical basis, it is nearly impossible to derive a general set of quality criteria for scientific work outside specific research traditions. Applied science introduces a new set of quality criteria having to do with the application of results in practical situations and policy making. A scientist doing basic research relates mainly to the scientific community of which he is a member, while in applied contract research the scientist has to consider the impact of his results both for the immediate users and upon interest groups possibly being affected. Application thus raises a whole new set of requirements having to do with business ethics, policy consequences and societal ethics in general.

  5. Applied Meteorology Unit (AMU)

    NASA Technical Reports Server (NTRS)

    Bauman, William; Lambert, Winifred; Wheeler, Mark; Barrett, Joe; Watson, Leela

    2007-01-01

    This report summarizes the Applied Meteorology Unit (AMU) activities for the second quarter of Fiscal Year 2007 (January - March 2007). Tasks reported on are: Obiective Lightning Probability Tool, Peak Wind Tool for General Forecasting, Situational Lightning Climatologies for Central Florida, Anvil Threat Corridor Forecast Tool in AWIPS, Volume Averaqed Heiqht lnteq rated Radar Reflectivity (VAHIRR), Tower Data Skew-t Tool, and Weather Research and Forecastini (WRF) Model Sensitivity Study

  6. Nanoengineering Applied to Tungsten

    DTIC Science & Technology

    2006-05-01

    and R. Z. Valiev ARL-RP- 123 May 2006 A reprint from the Proceedings of the Sixth International Conference on Tungsten, Refractory...Ground, MD 21005-5066 ARL-RP- 123 May 2006 Nanoengineering Applied to Tungsten Q. Wei University of North Carolina-Charlotte B. E...ORGANIZATION REPORT NUMBER ARL-RP- 123 10. SPONSOR/MONITOR’S ACRONYM(S) 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 11. SPONSOR

  7. Applied science. Introduction.

    PubMed

    Bud, Robert

    2012-09-01

    Such categories as applied science and pure science can be thought of as "ideological." They have been contested in the public sphere, exposing long-term intellectual commitments, assumptions, balances of power, and material interests. This group of essays explores the contest over applied science in Britain and the United States during the nineteenth century. The essays look at the concept in the context of a variety of neighbors, including pure science, technology, and art. They are closely related and connected to contemporary historiographic debate. Jennifer Alexander links the issues raised to a recent paper by Paul Forman. Paul Lucier and Graeme Gooday deal with the debates in the last quarter of the century in the United States and Britain, respectively. Robert Bud deals with the earlier part of the nineteenth century, with an eye specifically on the variety of concepts hybridized under the heading of "applied science." Eric Schatzberg looks at the erosion of the earlier concept of art. As a whole, the essays illuminate both long-term changes and nuanced debate and are themselves intended to provoke further reflection on science in the public sphere.

  8. Applied Meteorology Unit (AMU)

    NASA Technical Reports Server (NTRS)

    Bauman, William; Crawford, Winifred; Barrett, Joe; Watson, Leela; Wheeler, Mark

    2010-01-01

    This report summarizes the Applied Meteorology Unit (AMU) activities for the first quarter of Fiscal Year 2010 (October - December 2009). A detailed project schedule is included in the Appendix. Included tasks are: (1) Peak Wind Tool for User Launch Commit Criteria (LCC), (2) Objective Lightning Probability Tool, Phase III, (3) Peak Wind Tool for General Forecasting, Phase II, (4) Upgrade Summer Severe Weather Tool in Meteorological Interactive Data Display System (MIDDS), (5) Advanced Regional Prediction System (ARPS) Data Analysis System (ADAS) Update and Maintainability, (5) Verify 12-km resolution North American Model (MesoNAM) Performance, and (5) Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) Graphical User Interface.

  9. NASA Applied Sciences Program

    NASA Technical Reports Server (NTRS)

    Frederick, Martin

    2006-01-01

    This presentation highlights the NASA Applied Sciences Program. The goal of the program is to extend the results of scientific research and knowledge beyond the science community to contribute to NASA's partners' applications of national priority, such as agricultural efficiency, energy management and Homeland Security. Another purpose of the program's scientific research is to increase knowledge of the Earth-Sun system to enable improved predictions of climate, weather, and natural hazards. The program primarily optimizes benefits for citizens by contributing to partnering on applications that are used by state, local and tribal governments.

  10. Applied Meteorology Unit (AMU)

    NASA Technical Reports Server (NTRS)

    Bauman, William H., Jr.; Crawford, Winifred; Short, David; Barrett, Joe; Watson, Leela

    2008-01-01

    This report summarizes the Applied Meteorology Unit (AMU) activities for the second quarter of Fiscal Year 2008 (January - March 2008). Projects described are: (1) Peak Wind Tool for User Launch Commit Criteria (LCC), (2) Peak Wind Tool for General Forecasting, (3) Situational Lightning Climatologies for Central Florida. Phase III, (4) Volume Averaged Height Integrated Radar Reflectivity (VAHIRR), (5) Impact of Local Sensors, (6) Radar Scan Strategies for the PAFB WSR-74C Replacement and (7) WRF Wind Sensitivity Study at Edwards Air Force Base.

  11. Applied Impact Physics Research

    NASA Astrophysics Data System (ADS)

    Wickert, Matthias

    2013-06-01

    Applied impact physics research is based on the capability to examine impact processes for a wide range of impact conditions with respect to velocity as well as mass and shape of the projectile. For this reason, Fraunhofer EMI operates a large variety of launchers that address velocities up to ordnance velocities as single stage powder gun but which can also be operated as two-stage light gas guns achieving the regime of low earth orbital velocity. Thereby for projectile masses of up to 100 g hypervelocity impact phenomena up to 7.8 km/s can be addressed. Advanced optical diagnostic techniques like microsecond video are used as commercial systems but - since impact phenomena are mostly related with debris or dust - specialized diagnostics are developed in-house like x-ray cinematography and x-ray tomography. Selected topics of the field of applied impact physics will be presented like the interesting behavior of long rods penetrating low-density materials or experimental findings at hypervelocity for this class of materials as well as new x-ray diagnositic techniques.

  12. Applied Routh approximation

    NASA Technical Reports Server (NTRS)

    Merrill, W. C.

    1978-01-01

    The Routh approximation technique for reducing the complexity of system models was applied in the frequency domain to a 16th order, state variable model of the F100 engine and to a 43d order, transfer function model of a launch vehicle boost pump pressure regulator. The results motivate extending the frequency domain formulation of the Routh method to the time domain in order to handle the state variable formulation directly. The time domain formulation was derived and a characterization that specifies all possible Routh similarity transformations was given. The characterization was computed by solving two eigenvalue-eigenvector problems. The application of the time domain Routh technique to the state variable engine model is described, and some results are given. Additional computational problems are discussed, including an optimization procedure that can improve the approximation accuracy by taking advantage of the transformation characterization.

  13. NASA Applied Sciences Program

    NASA Technical Reports Server (NTRS)

    Estes, Sue M.; Haynes, J. A.

    2009-01-01

    NASA's strategic Goals: a) Develop a balanced overall program of science, exploration, and aeronautics consistent with the redirection of human spaceflight program to focus on exploration. b) Study Earth from space to advance scientific understanding and meet societal needs. NASA's partnership efforts in global modeling and data assimilation over the next decade will shorten the distance from observations to answers for important, leading-edge science questions. NASA's Applied Sciences program will continue the Agency's efforts in benchmarking the assimilation of NASA research results into policy and management decision-support tools that are vital for the Nation's environment, economy, safety, and security. NASA also is working with NOAH and inter-agency forums to transition mature research capabilities to operational systems, primarily the polar and geostationary operational environmental satellites, and to utilize fully those assets for research purposes.

  14. Applying robotics to HAZMAT

    NASA Technical Reports Server (NTRS)

    Welch, Richard V.; Edmonds, Gary O.

    1994-01-01

    The use of robotics in situations involving hazardous materials can significantly reduce the risk of human injuries. The Emergency Response Robotics Project, which began in October 1990 at the Jet Propulsion Laboratory, is developing a teleoperated mobile robot allowing HAZMAT (hazardous materials) teams to remotely respond to incidents involving hazardous materials. The current robot, called HAZBOT III, can assist in locating characterizing, identifying, and mitigating hazardous material incidents without risking entry team personnel. The active involvement of the JPL Fire Department HAZMAT team has been vital in developing a robotic system which enables them to perform remote reconnaissance of a HAZMAT incident site. This paper provides a brief review of the history of the project, discusses the current system in detail, and presents other areas in which robotics can be applied removing people from hazardous environments/operations.

  15. Applied antineutrino physics workshop.

    SciTech Connect

    Lund, James C.

    2008-01-01

    This workshop is the fourth one of a series that includes the Neutrino Geophysics Conference at Honolulu, Hawaii, which I attended in 2005. This workshop was organized by the Astro-Particle and Cosmology laboratory in the recently opened Condoret building of the University of Paris. More information, including copies of the presentations, on the workshop is available on the website: www.apc.univ-paris7.fr/AAP2007/. The workshop aims at opening neutrino physics to various fields such that it can be applied in geosciences, nuclear industry (reactor and spent fuel monitoring) and non-proliferation. The workshop was attended by over 60 people from Europe, USA, Asia and Brazil. The meeting was also attended by representatives of the Comprehensive nuclear-Test Ban Treaty (CTBT) and the International Atomic Energy Agency (IAEA). The workshop also included a workshop dinner on board of a river boat sailing the Seine river.

  16. Methods of applied dynamics

    NASA Technical Reports Server (NTRS)

    Rheinfurth, M. H.; Wilson, H. B.

    1991-01-01

    The monograph was prepared to give the practicing engineer a clear understanding of dynamics with special consideration given to the dynamic analysis of aerospace systems. It is conceived to be both a desk-top reference and a refresher for aerospace engineers in government and industry. It could also be used as a supplement to standard texts for in-house training courses on the subject. Beginning with the basic concepts of kinematics and dynamics, the discussion proceeds to treat the dynamics of a system of particles. Both classical and modern formulations of the Lagrange equations, including constraints, are discussed and applied to the dynamic modeling of aerospace structures using the modal synthesis technique.

  17. Applied computational aerodynamics

    SciTech Connect

    Henne, P.A.

    1990-01-01

    The present volume discusses the original development of the panel method, the mapping solutions and singularity distributions of linear potential schemes, the capabilities of full-potential, Euler, and Navier-Stokes schemes, the use of the grid-generation methodology in applied aerodynamics, subsonic airfoil design, inverse airfoil design for transonic applications, the divergent trailing-edge airfoil innovation in CFD, Euler and potential computational results for selected aerodynamic configurations, and the application of CFD to wing high-lift systems. Also discussed are high-lift wing modifications for an advanced-capability EA-6B aircraft, Navier-Stokes methods for internal and integrated propulsion system flow predictions, the use of zonal techniques for analysis of rotor-stator interaction, CFD applications to complex configurations, CFD applications in component aerodynamic design of the V-22, Navier-Stokes computations of a complete F-16, CFD at supersonic/hypersonic speeds, and future CFD developments.

  18. Lessons learned and applied

    PubMed Central

    Hebert, Corey Joseph; Hall, Corey M.; Odoms, La’ Nyia J.

    2012-01-01

    Most vaccines available in the United States (US) have been incorporated into vaccination schedules for infants and young children, age groups particularly at risk of contracting infectious diseases. High universal vaccination coverage is responsible for substantially reducing or nearly eliminating many of the diseases that once killed thousands of children each year in the US. Despite the success of infant vaccinations, periods of low vaccination coverage and the limited immunogenicity and duration of protection of certain vaccines have resulted in sporadic outbreaks, allowing some diseases to spread in communities. These challenges suggest that expanded vaccination coverage to younger infants and adolescents, and more immunogenic vaccines, may be needed in some instances. This review focuses on the importance of infant immunization and explores the successes and challenges of current early childhood vaccination programs and how these lessons may be applied to other invasive diseases, such as meningococcal disease. PMID:22617834

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

    PubMed

    Lu, Lu; Huang, Xirong; Qu, Yinbo

    2011-10-01

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

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

    SciTech Connect

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

    2008-02-15

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

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

    DOE PAGES

    Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.; ...

    2016-10-12

    Ag7Fe3(P2O7 )4 is an example of an electrochemical displacement material which contains two different electrochemically active metal cations, where one cation (Ag+) forms metallic silver nanoparticles external to the crystals of Ag7Fe3(P2O7 )4 via an electrochemical reduction displacement reaction, while the other cation (Fe+3) is electrochemically reduced with the retention of iron cations within the anion structural framework concomitant with lithium insertion. These contrasting redox chemistries within one pure cathode material enable high rate capability and reversibility when Ag7Fe3(P2O7 )4 is employed as cathode material in a lithium ion battery (LIB). Further, pyrophosphate materials are thermally and electrically stable, desirablemore » attributes for cathode materials in LIBs. In this article, a bimetallic pyrophosphate material Ag7Fe3(P2O7 )4 is synthesized and confirmed to be a single phase by Rietveld refinement. Electrochemistry of Ag7Fe3(P2O7 )4 is reported for the first time in the context of lithium based batteries using cyclic voltammetry and galvanostatic discharge–charge cycling. The reduction displacement reaction and the lithium (de)insertion processes are investigated using ex situ X-ray absorption spectroscopy and X-ray diffraction of electrochemically reduced and oxidized Ag7Fe3(P2O7 )4. Ag7Fe3(P2O7 )4 exhibits good reversibility at the iron centers indicated by ~80% capacity retention over 100 cycles following the initial formation cycle and excellent rate capability exhibited by ~70% capacity retention upon a 4-fold increase in current.« less

  2. Syntheses, Structures, and Electrochemistry of the Defective ccp [Pt33(CO)38](2-) and the bcc [Pt40(CO)40](6-) Molecular Nanoclusters.

    PubMed

    Cattabriga, Enrico; Ciabatti, Iacopo; Femoni, Cristina; Funaioli, Tiziana; Iapalucci, Maria Carmela; Zacchini, Stefano

    2016-06-20

    The molecular [Pt33(CO)38](2-) nanocluster was obtained from the thermal decomposition of Na2[Pt15(CO)30] in methanol. The reaction of [Pt19(CO)22](4-) with acids (1-2 equiv) affords the unstable [Pt19(CO)22](3-) trianion, which evolves with time leading eventually to the [Pt40(CO)40](6-) hexa-anion. The total structures of both nanoclusters were determined via single-crystal X-ray diffraction. [Pt33(CO)38](2-) displays a defective ccp Pt33 core and shows that localized deformations occur in correspondence of atomic defects to "repair" them. In contrast, [Pt40(CO)40](6-) shows a bcc Pt40 core and represents the largest Pt cluster with a body-centered structure. The rich electrochemistry of the two high-nuclearity platinum carbonyl clusters was studied by cyclic voltammetry and electrochemical in situ Fourier transform infrared spectroscopy. The redox changes of [Pt33(CO)38](2-) show features of chemical reversibility and electrochemical quasi-reversibility, and the vibrational spectra in the CO stretching region of the nine redox forms of the cluster [Pt33(CO)38](n) (n = 0 to -4, -6 to -9) are reported. Almost all the redox processes exhibited by [Pt40(CO)40](6-) are chemically and electrochemically reversible, and the eight oxidation states of [Pt40(CO)40] from -4 to -11 were spectroscopically characterized. The effect of the more regular bcc Pt-carbonyl cluster structure of [Pt40(CO)40](6-) with respect to that of the defective ccp Pt33 core on the redox behavior is discussed.

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

    PubMed

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

    2010-08-01

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

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

    PubMed

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

    2015-04-15

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

  5. Electrochemistry of the antibacterial and antifungal drug nitroxoline and its determination in bulk form, pharmaceutical formulation and human blood.

    PubMed

    Ghoneim, Mohamed M; El-Desoky, Hanaa S; Abdel-Galeil, Mohamed M

    2011-02-01

    Nitroxoline has been reduced at the mercury electrode in buffered solutions (pH 2-11) in two irreversible cathodic steps. The first step was attributed to reduction of -NO(2) group to the hydroxylamine stage and the second one to reduction-saturation of the C=N double bond. DC-polarographic and various adsorptive stripping voltammetric methods were developed for determination of nitroxoline in bulk form. Limits of quantitation of 1.02×10(-6), 3.05×10(-8), 9.01×10(-9), and 9.12×10(-10)M nitroxoline were achieved by means of the developed DC-polarography, differential-pulse-, linear-sweep-, and square-wave-adsorptive cathodic stripping voltammetric methods, respectively. All these electroanalytical methods were successfully applied for determination of nitroxoline in its Nibiol(®) tablets. While only the developed adsorptive stripping voltammetry methods were successfully applied for determination of the drug in spiked human serum and for pharmacokinetic studies in real human plasma. The analysis was carried out without interference from common excipients and without the necessity for prior extraction or interaction with any reagent during the analysis.

  6. Applying Evolutionary Anthropology

    PubMed Central

    Gibson, Mhairi A; Lawson, David W

    2015-01-01

    Evolutionary anthropology provides a powerful theoretical framework for understanding how both current environments and legacies of past selection shape human behavioral diversity. This integrative and pluralistic field, combining ethnographic, demographic, and sociological methods, has provided new insights into the ultimate forces and proximate pathways that guide human adaptation and variation. Here, we present the argument that evolutionary anthropological studies of human behavior also hold great, largely untapped, potential to guide the design, implementation, and evaluation of social and public health policy. Focusing on the key anthropological themes of reproduction, production, and distribution we highlight classic and recent research demonstrating the value of an evolutionary perspective to improving human well-being. The challenge now comes in transforming relevance into action and, for that, evolutionary behavioral anthropologists will need to forge deeper connections with other applied social scientists and policy-makers. We are hopeful that these developments are underway and that, with the current tide of enthusiasm for evidence-based approaches to policy, evolutionary anthropology is well positioned to make a strong contribution. PMID:25684561

  7. Applying microfluidics to electrophysiology.

    PubMed

    Eddington, David T

    2007-01-01

    Microfluidics can be integrated with standard electrophysiology techniques to allow new experimental modalities. Specifically, the motivation for the microfluidic brain slice device is discussed including how the device docks to standard perfusion chambers and the technique of passive pumping which is used to deliver boluses of neuromodulators to the brain slice. By simplifying the device design, we are able to achieve a practical solution to the current unmet electrophysiology need of applying multiple neuromodulators across multiple regions of the brain slice. This is achieved by substituting the standard coverglass substrate of the perfusion chamber with a thin microfluidic device bonded to the coverglass substrate. This was then attached to the perfusion chamber and small holes connect the open-well of the perfusion chamber to the microfluidic channels buried within the microfluidic substrate. These microfluidic channels are interfaced with ports drilled into the edge of the perfusion chamber to access and deliver stimulants. This project represents how the field of microfluidics is transitioning away from proof-of concept device demonstrations and into practical solutions for unmet experimental and clinical needs.

  8. Applying evolutionary anthropology.

    PubMed

    Gibson, Mhairi A; Lawson, David W

    2015-01-01

    Evolutionary anthropology provides a powerful theoretical framework for understanding how both current environments and legacies of past selection shape human behavioral diversity. This integrative and pluralistic field, combining ethnographic, demographic, and sociological methods, has provided new insights into the ultimate forces and proximate pathways that guide human adaptation and variation. Here, we present the argument that evolutionary anthropological studies of human behavior also hold great, largely untapped, potential to guide the design, implementation, and evaluation of social and public health policy. Focusing on the key anthropological themes of reproduction, production, and distribution we highlight classic and recent research demonstrating the value of an evolutionary perspective to improving human well-being. The challenge now comes in transforming relevance into action and, for that, evolutionary behavioral anthropologists will need to forge deeper connections with other applied social scientists and policy-makers. We are hopeful that these developments are underway and that, with the current tide of enthusiasm for evidence-based approaches to policy, evolutionary anthropology is well positioned to make a strong contribution.

  9. Essays in applied microeconomics

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoting

    In this dissertation I use Microeconomic theory to study firms' behavior. Chapter One introduces the motivations and main findings of this dissertation. Chapter Two studies the issue of information provision through advertisement when markets are segmented and consumers' price information is incomplete. Firms compete in prices and advertising strategies for consumers with transportation costs. High advertising costs contribute to market segmentation. Low advertising costs promote price competition among firms and improves consumer welfare. Chapter Three also investigates market power as a result of consumers' switching costs. A potential entrant can offer a new product bundled with an existing product to compensate consumers for their switching cost. If the primary market is competitive, bundling simply plays the role of price discrimination, and it does not dominate unbundled sales in the process of entry. If the entrant has market power in the primary market, then bundling also plays the role of leveraging market power and it dominates unbundled sales. The market for electric power generation has been opened to competition in recent years. Chapter Four looks at issues involved in the deregulated electricity market. By comparing the performance of the competitive market with the social optimum, we identify the conditions under which market equilibrium generates socially efficient levels of electric power. Chapter Two to Four investigate the strategic behavior among firms. Chapter Five studies the interaction between firms and unemployed workers in a frictional labor market. We set up an asymmetric job auction model, where two types of workers apply for two types of job openings by bidding in auctions and firms hire the applicant offering them the most profits. The job auction model internalizes the determination of the share of surplus from a match, therefore endogenously generates incentives for an efficient division of the matching surplus. Microeconomic

  10. Applied Historical Astronomy

    NASA Astrophysics Data System (ADS)

    Stephenson, F. Richard

    2014-01-01

    F. Richard Stephenson has spent most of his research career -- spanning more than 45 years -- studying various aspects of Applied Historical Astronomy. The aim of this interdisciplinary subject is the application of historical astronomical records to the investigation of problems in modern astronomy and geophysics. Stephenson has almost exclusively concentrated on pre-telescopic records, especially those preserved from ancient and medieval times -- the earliest reliable observations dating from around 700 BC. The records which have mainly interested him are of eclipses (both solar and lunar), supernovae, sunspots and aurorae, and Halley's Comet. The main sources of early astronomical data are fourfold: records from ancient and medieval East Asia (China, together with Korea and Japan); ancient Babylon; ancient and medieval Europe; and the medieval Arab world. A feature of Stephenson's research is the direct consultation of early astronomical texts in their original language -- either working unaided or with the help of colleagues. He has also developed a variety of techniques to help interpret the various observations. Most pre-telescopic observations are very crude by present-day standards. In addition, early motives for skywatching were more often astrological rather than scientific. Despite these drawbacks, ancient and medieval astronomical records have two remarkable advantages over modern data. Firstly, they can enable the investigation of long-term trends (e.g. in the terrestrial rate of rotation), which in the relatively short period covered by telescopic observations are obscured by short-term fluctuations. Secondly, over the lengthy time-scale which they cover, significant numbers of very rare events (such as Galactic supernovae) were reported, which have few -- if any-- counterparts in the telescopic record. In his various researches, Stephenson has mainly focused his attention on two specific topics. These are: (i) long-term changes in the Earth's rate of

  11. Applied large eddy simulation.

    PubMed

    Tucker, Paul G; Lardeau, Sylvain

    2009-07-28

    Large eddy simulation (LES) is now seen more and more as a viable alternative to current industrial practice, usually based on problem-specific Reynolds-averaged Navier-Stokes (RANS) methods. Access to detailed flow physics is attractive to industry, especially in an environment in which computer modelling is bound to play an ever increasing role. However, the improvement in accuracy and flow detail has substantial cost. This has so far prevented wider industrial use of LES. The purpose of the applied LES discussion meeting was to address questions regarding what is achievable and what is not, given the current technology and knowledge, for an industrial practitioner who is interested in using LES. The use of LES was explored in an application-centred context between diverse fields. The general flow-governing equation form was explored along with various LES models. The errors occurring in LES were analysed. Also, the hybridization of RANS and LES was considered. The importance of modelling relative to boundary conditions, problem definition and other more mundane aspects were examined. It was to an extent concluded that for LES to make most rapid industrial impact, pragmatic hybrid use of LES, implicit LES and RANS elements will probably be needed. Added to this further, highly industrial sector model parametrizations will be required with clear thought on the key target design parameter(s). The combination of good numerical modelling expertise, a sound understanding of turbulence, along with artistry, pragmatism and the use of recent developments in computer science should dramatically add impetus to the industrial uptake of LES. In the light of the numerous technical challenges that remain it appears that for some time to come LES will have echoes of the high levels of technical knowledge required for safe use of RANS but with much greater fidelity.

  12. Essays in Applied Microeconomics

    NASA Astrophysics Data System (ADS)

    Ge, Qi

    This dissertation consists of three self-contained applied microeconomics essays on topics related to behavioral economics and industrial organization. Chapter 1 studies how sentiment as a result of sports event outcomes affects consumers' tipping behavior in the presence of social norms. I formulate a model of tipping behavior that captures consumer sentiment following a reference-dependent preference framework and empirically test its relevance using the game outcomes of the NBA and the trip and tipping data on New York City taxicabs. While I find that consumers' tipping behavior responds to unexpected wins and losses of their home team, particularly in close game outcomes, I do not find evidence for loss aversion. Coupled with the findings on default tipping, my empirical results on the asymmetric tipping responses suggest that while social norms may dominate loss aversion, affect and surprises can result in freedom on the upside of tipping. Chapter 2 utilizes a novel data source of airline entry and exit announcements and examines how the incumbent airlines adjust quality provisions as a response to their competitors' announcements and the role of timing in such responses. I find no evidence that the incumbents engage in preemptive actions when facing probable entry and exit threats as signaled by the competitors' announcements in either short term or long term. There is, however, evidence supporting their responses to the competitors' realized entry or exit. My empirical findings underscore the role of timing in determining preemptive actions and suggest that previous studies may have overestimated how the incumbent airlines respond to entry threats. Chapter 3, which is collaborated with Benjamin Ho, investigates the habit formation of consumers' thermostat setting behavior, an often implicitly made decision and yet a key determinant of home energy consumption and expenditures. We utilize a high frequency dataset on household thermostat usage and find that

  13. Essays in applied economics

    NASA Astrophysics Data System (ADS)

    Arano, Kathleen

    Three independent studies in applied economics are presented. The first essay looks at the US natural gas industrial sector and estimates welfare effects associated with the changes in natural gas regulatory policy over the past three decades. Using a disequilibrium model suited to the natural gas industry, welfare transfers and deadweight losses are calculated. Results indicate that deregulation policies, beginning with the NGPA of 1978, have caused the industry to become more responsive to market conditions. Over time, regulated prices converge toward the estimated equilibrium prices. As a result of this convergence, deadweight losses associated with regulation are also diminished. The second essay examines the discounted utility model (DU), the standard model used for intertemporal decision-making. Prior empirical studies challenge the descriptive validity of the model. This essay addresses the four main inconsistencies that have been raised: domain dependence, magnitude effects, time effects, and gain/loss asymmetries. These inconsistencies, however, may be the result of the implicit assumption of linear utility and not a failure of the DU model itself. In order to test this hypothesis, data was collected from in-class surveys of economics classes at Mississippi State University. A random effects model for panel data estimation which accounts for individual specific effects was then used to impute discount rates measured in terms of dollars and utility. All four inconsistencies were found to be present when the dollar measures were used. Using utility measures of the discount rate resolved the inconsistencies in some cases. The third essay brings together two perspectives in the study of religion and economics: modeling religious behavior using economic tools and variables, and modeling economic behavior using religious variables. A system of ordered probit equations is developed to simultaneously model religious activities and economic outcomes. Using data

  14. Applied physiology of swimming.

    PubMed

    Lavoie, J M; Montpetit, R R

    1986-01-01

    Scientific research in swimming over the past 10 to 15 years has been oriented toward multiple aspects that relate to applied and basic physiology, metabolism, biochemistry, and endocrinology. This review considers recent findings on: 1) specific physical characteristics of swimmers; 2) the energetics of swimming; 3) the evaluation of aerobic fitness in swimming; and 4) some metabolic and hormonal aspects related to swimmers. Firstly, the age of finalists in Olympic swimming is not much different from that of the participants from other sports. They are taller and heavier than a reference population of the same age. The height bias in swimming may be the reason for lack of success from some Asian and African countries. Experimental data point toward greater leanness, particularly in female swimmers, than was seen 10 years ago. Overall, female swimmers present a range of 14 to 19% body fat whereas males are much lower (5 to 10%). Secondly, the relationship between O2 uptake and crawl swimming velocity (at training and competitive speeds) is thought to be linear. The energy cost varies between strokes with a dichotomy between the 2 symmetrical and the 2 asymmetrical strokes. Energy expenditure in swimming is represented by the sum of the cost of translational motion (drag) and maintenance of horizontal motion (gravity). The cost of the latter decreases as speed increases. Examination of the question of size-associated effects on the cost of swimming using Huxley's allometric equation (Y = axb) shows an almost direct relationship with passive drag. Expressing energy cost in litres of O2/m/kg is proposed as a better index of technical swimming ability than the traditional expression of VO2/distance in L/km. Thirdly, maximal direct conventional techniques used to evaluate maximal oxygen consumption (VO2 max) in swimming include free swimming, tethered swimming, and flume swimming. Despite the individual peculiarities of each method, with similar experimental conditions

  15. Using Implicit Solvent in Ab Initio Electrochemical Modeling: Investigating Li⁺/Li Electrochemistry at a Li/Solvent Interface.

    PubMed

    Lespes, Nicolas; Filhol, Jean-Sébastien

    2015-07-14

    This paper focuses on the use of implicit solvent in electrochemical density functional theory (DFT) calculations. We investigate both the necessity and limits of an implicit solvent polarizable continuum model (PCM). In order to recover the proper electrochemical behavior of the surface and, in particular, a proper potential scale, the solvent model is determined to be mandatory: in the limit of a high dielectric constant, the surface capacitance becomes independent of the interslab space used in the model and, therefore, the electrochemical properties become intrinsic of the interface structure. We show that the computed surface capacitance is not only dependent on the implicit solvent dielectric constant, but also on the solvent cavity parameter that should be precisely tuned. This model is then applied to the Li/electrolyte interface in order to check its ability to compute thermodynamic equilibrium properties. The use of a purely implicit solvent approach allows the recovery of a more reasonable equilibrium potential for the Li(+)/Li redox pair, compared to vacuum approaches, but a potential that it is still off by 1.5 V. Then, the inclusion of explicit solvent molecules improves the description of the solvent-Li(+) chemical bond in the first solvation shell and allows recovery of the experimental value within 100 mV. Finally, we show that the redox active center involves the first solvation shell of Li(+), suggesting a particular pathway for the observed solvent dissociation in Li-ion batteries.

  16. Direct electrochemistry of horseradish peroxidase immobilized on the layered calcium carbonate-gold nanoparticles inorganic hybrid composite.

    PubMed

    Li, Feng; Feng, Yan; Wang, Zhen; Yang, Limin; Zhuo, Linhai; Tang, Bo

    2010-06-15

    A mediator-free hydrogen peroxide (H(2)O(2)) biosensor was fabricated based on immobilization of horseradish peroxidase (HRP) on layered calcium carbonate-gold nanoparticles (CaCO(3)-AuNPs) inorganic hybrid composite. The proposed biosensor showed a strong electrocatalytic activity toward the reduction of H(2)O(2), which could be attributed to the favored orientation of HRP in the well-confined surface as well as the high electrical conductivity of the resulting CaCO(3)-AuNPs inorganic hybrid composite. The hybrid composite was obtained by the adsorption of AuNPs onto the surfaces of layered CaCO(3) through electrostatic interaction. The key analytical parameters relative to the biosensor performance such as pH and applied potential were optimized. The developed biosensor also exhibited a fast amperometric response (3s), a good linear response toward H(2)O(2) over a wide range of concentration from 5.0x10(-7) to 5.2x10(-3)M, and a low detection limit of 1.0x10(-7)M. The facile, inexpensive and reliable sensing platform based on layered CaCO(3)-AuNPs inorganic hybrid composite should hold a huge potential for the fabrication of more other biosensors.

  17. Modeling of electrochemistry and steam-methane reforming performance for simulating pressurized solid oxide fuel cell stacks

    NASA Astrophysics Data System (ADS)

    Recknagle, Kurtis P.; Ryan, Emily M.; Koeppel, Brian J.; Mahoney, Lenna A.; Khaleel, Moe A.

    This paper examines the electrochemical and direct internal steam-methane reforming performance of the solid oxide fuel cell when subjected to pressurization. Pressurized operation boosts the Nernst potential and decreases the activation polarization, both of which serve to increase cell voltage and power while lowering the heat load and operating temperature. A model considering the activation polarization in both the fuel and the air electrodes was adopted to address this effect on the electrochemical performance. The pressurized methane conversion kinetics and the increase in equilibrium methane concentration are considered in a new rate expression. The models were then applied in simulations to predict how the distributions of direct internal reforming rate, temperature, and current density are effected within stacks operating at elevated pressure. A generic 10 cm counter-flow stack model was created and used for the simulations of pressurized operation. The predictions showed improved thermal and electrical performance with increased operating pressure. The average and maximum cell temperatures decreased by 3% (20 °C) while the cell voltage increased by 9% as the operating pressure was increased from 1 to 10 atm.

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

    PubMed

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

    2009-12-15

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

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

    PubMed

    Chekin, Fereshteh; Gorton, Lo; Tapsobea, Issa

    2015-01-01

    This study compares the behaviour of direct and mediated electrochemistry of horseradish peroxidase (HRP) immobilised on screen-printed carbon electrodes (SPCEs), screen-printed carbon electrodes modified with carboxyl-functionalised multi-wall carbon nanotubes (MWCNT-SPCEs) and screen-printed carbon electrodes modified with carboxyl-functionalised single-wall carbon nanotubes (SWCNT-SPCEs). The techniques of cyclic voltammetry and amperometry in the flow mode were used to characterise the properties of the HRP immobilised on screen-printed electrodes. From measurements of the mediated and mediatorless currents of hydrogen peroxide reduction at the HRP-modified electrodes, it was concluded that the fraction of enzyme molecules in direct electron transfer (DET) contact with the electrode varies substantially for the different electrodes. It was observed that the screen-printed carbon electrodes modified with carbon nanotubes (MWCNT-SPCEs and SWCNT-SPCEs) demonstrated a substantially higher percentage (≈100 %) of HRP molecules in DET contact than the screen-printed carbon electrodes (≈60 %). The HRP-modified electrodes were used for determination of hydrogen peroxide in mediatorless mode. The SWCNT-SPCE gave the lowest detection limit (0.40 ± 0.09 μM) followed by MWCNT-SPCE (0.48 ± 0.07 μM) and SPCE (0.98 ± 0.2 μM). These modified electrodes were additionally developed for amperometric determination of phenolic compounds. It was found that the SWCNT-SPCE gave a detection limit for catechol of 110.2 ± 3.6 nM, dopamine of 640.2 ± 9.2 nM, octopamine of 3341 ± 15 nM, pyrogallol of 50.10 ± 2.9 nM and 3,4-dihydroxy-L-phenylalanine of 980.7 ± 8.7 nM using 50 μM H2O2 in the flow carrier.

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

    NASA Astrophysics Data System (ADS)

    Hawkins, Ian C.

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

  1. Synthesis, Structure, Electrochemistry, and Spectral Characterization of Bis-Isatin Thiocarbohydrazone Metal Complexes and Their Antitumor Activity Against Ehrlich Ascites Carcinoma in Swiss Albino Mice

    PubMed Central

    Sathisha, M. P.; Revankar, V. K.; Pai, K. S. R.

    2008-01-01

    The synthesis, structure, electrochemistry, and biological studies of Co(II), Ni(II), Cu(II), and Zn(II) complexes of thiocarbohydrazone ligand are described. The ligand is synthesized starting from thiocarbohydrazide and isatin. It is evident from the IR data that in all the complexes, only one part of the ligand is coordinated to the metal ion resulting mononuclear complexes. The ligand coordinates essentially through the carbonyl oxygen of the isatin fragment, the nitrogen atom of the azomethine group, and sulfur atom after deprotonation to give five membered rings. H1 NMR spectrum of the ligand shows only one set of signals for the aromatic protons, while the NH of isatin and NH of hydrazone give rise to two different singlets in the 11–14 ppm range. The formulations, [Cu(L)Cl]·2H2O, [Cu(L)(CH3COO)]·2H2O, [Ni(L)Cl], [Ni(L)(CH3COO)], [Co(L2)], and [Zn(L2)]·2H2O are in accordance with elemental analyses, physical, and spectroscopic measurements. The complexes are soluble in organic solvents. Molar conductance values in DMF indicate the nonelectrolytic nature of the complexes. Copper complex displays quasireversible cyclic voltametric responses with Ep near −0.659 v and 0.504 v Vs Ag/AgCl at the scan rate of 0.1 V/s. Copper(II) complexes show a single line EPR signals. For the observed magnetic moment and electronic spectral data possible explanation has been discussed. From all the available data, the probable structures for the complexes have been proposed. The compounds synthesized in present study have shown promising cytotoxic activity when screened using the in vitro method and at the same time were shown to have good activity when tested using the Ehrlich ascites carcinoma (EAC) model. The antimicrobial screening showed that the cobalt complex possesses enhanced antimicrobial activity towards fungi. PMID:18320020

  2. Silver vanadium diphosphate Ag{sub 2}VP{sub 2}O{sub 8}: Electrochemistry and characterization of reduced material providing mechanistic insights

    SciTech Connect

    Takeuchi, Esther S.; Lee, Chia-Ying; Cheng, Po-Jen; Menard, Melissa C.; Marschilok, Amy C.; Takeuchi, Kenneth J.

    2013-04-15

    Silver vanadium phosphorous oxides (Ag{sub w}V{sub x}P{sub y}O{sub z}) are notable battery cathode materials due to their high energy density and demonstrated ability to form in-situ Ag metal nanostructured electrically conductive networks within the cathode. While analogous silver vanadium diphosphate materials have been prepared, electrochemical evaluations of these diphosphate based materials have been limited. We report here the first electrochemical study of a silver vanadium diphosphate, Ag{sub 2}VP{sub 2}O{sub 8}, where the structural differences associated with phosphorous oxides versus diphosphates profoundly affect the associated electrochemistry. Reminiscent of Ag{sub 2}VO{sub 2}PO{sub 4} reduction, in-situ formation of silver metal nanoparticles was observed with reduction of Ag{sub 2}VP{sub 2}O{sub 8}. However, counter to Ag{sub 2}VO{sub 2}PO{sub 4} reduction, Ag{sub 2}VP{sub 2}O{sub 8} demonstrates a significant decrease in conductivity upon continued electrochemical reduction. Structural analysis contrasting the crystallography of the parent Ag{sub 2}VP{sub 2}O{sub 8} with that of the proposed Li{sub 2}VP{sub 2}O{sub 8} reduction product is employed to gain insight into the observed electrochemical reduction behavior, where the structural rigidity associated with the diphosphate anion may be associated with the observed particle fracturing upon deep electrochemical reduction. Further, the diphosphate anion structure may be associated with the high thermal stability of the partially reduced Ag{sub 2}VP{sub 2}O{sub 8} materials, which bodes well for enhanced safety of batteries incorporating this material. - Graphical abstract: Structure and galvanostatic intermittent titration-type test data for silver vanadium diphosphate, Ag{sub 2}VP{sub 2}O{sub 8}. Highlights: ► First electrochemical study of a silver vanadium diphosphate, Ag{sub 2}VP{sub 2}O{sub 8}. ► In-situ formation of Ag{sup 0} nanoparticles was observed upon electrochemical reduction.

  3. Electrochemistry and structure of the conducting polymer poly-[3-(4-fluorophenyl)thiophene] used in electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Herbert, Jesse James

    2000-10-01

    Electronically conducting polymers can be doped (ionic absorption into polymer matrix) and dedoped at high-power rates and to high energy densities. With lower cost predictions than for high power batteries or noble metal oxide pseudocapacitors, yet with similar energy densities, these are potential active materials for use in electrochemical supercapacitors. Paramount to the use of these materials in deep charge and discharge duty cycles is their achievement of high cycle life with very little loss in capacitance or charge/discharge efficiency. This dissertation explores several aspects of the poly-[3-(4-fluorophenyl)thiophene] (PFPT) conducting polymer with a modifying additive, 3,3 bithiophene (BT). Electrochemical investigation is combined with material science characterization to provide new insights and information on this material in a manner that could not be achieved if only one of these approaches were applied. Specifically, implications of cycling this material with delays or rest periods inserted in the deep cycling routines are explored. Significant reductions in capacitance are observed after only a couple dozen cycles, compared to the same cycle routines with no rest periods. This reduced capacitance effect may have other causes unrelated to the lag cycling however and represents an area for further research. Electrochemical Cycling is shown to induce structural changes such as 'melting' or smoothing which modify the surface area of the copolymer. These results are discussed in relation to some more general theoretical findings for polyampholytes and high surface area polymers which suggest that the ionic cycling may contribute to the smoothing behavior. Atomic force microscopy (AFM) studies reveal greater numbers of nucleation sites during growth of the new high surface structure of the additive modified PFPT/BT (copolymer). Additionally, such films are smoother at first (as previously reported elsewhere), but undergo a transition to the high

  4. The Routledge Applied Linguistics Reader

    ERIC Educational Resources Information Center

    Wei, Li, Ed.

    2011-01-01

    "The Routledge Applied Linguistics Reader" is an essential collection of readings for students of Applied Linguistics. Divided into five sections: Language Teaching and Learning, Second Language Acquisition, Applied Linguistics, Identity and Power and Language Use in Professional Contexts, the "Reader" takes a broad…

  5. The Fleming Applied Projects Program

    ERIC Educational Resources Information Center

    Spasov, Peter

    2004-01-01

    Applied Projects is a program where every technology student engages in an intensive team project full time during the final academic semester. A wide range of enterprises provide the real-world problems that form the basis of student projects. This article describes the program and how Fleming College uses this program for applied research. To…

  6. An Option in Applied Microbiology.

    ERIC Educational Resources Information Center

    Lee, William E., III

    1988-01-01

    Describes a program option for undergraduate chemical engineering students interested in biotechnology. Discusses how this program is deployed at the University of Southern Florida. Lists courses which apply to this program. Discusses the goals of teaching applied microbiology to engineering majors. (CW)

  7. Development of the Applied Baccalaureate

    ERIC Educational Resources Information Center

    Townsend, Barbara K.; Bragg, Debra D.; Ruud, Collin M.

    2009-01-01

    Increasing demands for economic competitiveness and educational effectiveness have led states and institutions to implement new approaches to facilitating baccalaureate completion. This study examined one of these approaches, the applied baccalaureate degree, which is designed to incorporate applied associate course work and degrees once…

  8. ELECTROCHEMISTRY OF FUEL CELL ELECTRODES.

    DTIC Science & Technology

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

  9. Electrochemistry at the Molecular Level.

    DTIC Science & Technology

    1983-12-01

    Ill. are well known and now exvertial specular reflectance ird~ aied spe,trowopy is firmly established. Thus. irneracton betweer. electrochers- issrv and...8217. >- 4. 04 4, 0 : .0 A’~..o 4.4 >l 4- , wn C Q, (a. , lC .) o 41, *- 2 O - - 0 ~ 4. ’ 4 4 4 1 - 0 01 1 . 4 10 %-. GO-- m 4 Q’. CL( 0 wC. 0 0 InC04 44 0 0...er is tne natur- -f n -- 𔃾 ~ ~ o -- c7rte a ~s ;y’ r soon as 4 fenn- - r - a -z -et of fusoon. ai ic C" v3r~ --3 t .r7eratur e, c --ial- StaitJlity

  10. Electrochemistry of Q-Graphene

    NASA Astrophysics Data System (ADS)

    Randviir, Edward P.; Brownson, Dale A. C.; Gómez-Mingot, Maria; Kampouris, Dimitrios K.; Iniesta, Jesús; Banks, Craig E.

    2012-09-01

    A newly synthesised type of graphene, Q-Graphene, has been physically and electrochemically characterised with Scanning and Transmission Electron Microscopy (SEM, TEM), X-ray Photoelectron Spectroscopy (XPS) and Cyclic Voltammetry (CV). Interpretation of SEM, TEM and XPS data reveal the material to consist of hollow carbon nanospheres of multi-layer graphene (viz. graphite), which exhibit a total oxygen content of ca. 36.0% (atomic weight via XPS). In addition to the carbon structures present, spherical magnesium oxide particles of <=50 nm in diameter are abundantly present in the sample (ca. 16.2%). Interestingly, although the TEM/SEM images show macroporous carbon structures, Raman spectroscopy shows peaks typically characteristic of graphene, which suggests the material is highly heterogeneous and consists of many types of carbon allotropes. Q-Graphene is electrochemically characterised using both inner-sphere and outer-sphere electrochemical redox probes, namely potassium ferrocyanide(ii), hexaammine-ruthenium(iii) chloride and hexachloroiridate(iii), in addition to the biologically relevant and electroactive analytes, norepinephrine, β-nicotinamide adenine dinucleotide (NADH) and l-ascorbic acid. The electrochemical response of Q-Graphene is benchmarked against edge plane- and basal plane-pyrolytic graphite (EPPG and BPPG respectively), pristine graphene and graphite alternatives. Q-Graphene is found to exhibit fast electron transfer kinetics, likely due to its high proportion of folded edges and surface defects, exhibiting a response similar to that of EPPG - which exhibits fast electron transfer rates due to the high proportion of edge plane sites it possesses. Furthermore, we demonstrate that the specific oxygen content plays a pivotal role in dictating the observed electrochemical response, which is analyte dependant. Consequently there is potential for this new member of the graphene family to be beneficially utilised in various electrochemical applications.A newly synthesised type of graphene, Q-Graphene, has been physically and electrochemically characterised with Scanning and Transmission Electron Microscopy (SEM, TEM), X-ray Photoelectron Spectroscopy (XPS) and Cyclic Voltammetry (CV). Interpretation of SEM, TEM and XPS data reveal the material to consist of hollow carbon nanospheres of multi-layer graphene (viz. graphite), which exhibit a total oxygen content of ca. 36.0% (atomic weight via XPS). In addition to the carbon structures present, spherical magnesium oxide particles of <=50 nm in diameter are abundantly present in the sample (ca. 16.2%). Interestingly, although the TEM/SEM images show macroporous carbon structures, Raman spectroscopy shows peaks typically characteristic of graphene, which suggests the material is highly heterogeneous and consists of many types of carbon allotropes. Q-Graphene is electrochemically characterised using both inner-sphere and outer-sphere electrochemical redox probes, namely potassium ferrocyanide(ii), hexaammine-ruthenium(iii) chloride and hexachloroiridate(iii), in addition to the biologically relevant and electroactive analytes, norepinephrine, β-nicotinamide adenine dinucleotide (NADH) and l-ascorbic acid. The electrochemical response of Q-Graphene is benchmarked against edge plane- and basal plane-pyrolytic graphite (EPPG and BPPG respectively), pristine graphene and graphite alternatives. Q-Graphene is found to exhibit fast electron transfer kinetics, likely due to its high proportion of folded edges and surface defects, exhibiting a response similar to that of EPPG - which exhibits fast electron transfer rates due to the high proportion of edge plane sites it possesses. Furthermore, we demonstrate that the specific oxygen content plays a pivotal role in dictating the observed electrochemical response, which is analyte dependant. Consequently there is potential for this new member of the graphene family to be beneficially utilised in various electrochemical applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr31823g

  11. Semiconductor electrochemistry of coal pyrite

    SciTech Connect

    Osseo-Asare, K.; Wei, D.

    1992-01-01

    The kinetics of the formation of Fe(HS)[sup 2]-n[sub n,] the intermediate in the formation of FeS (from the reaction between aqueous sulfide ions and dissolved FE(II) salts) was studied with a stopped-flow spectrophotometric technique. As described in the previous report, the absorbance-time curve indicated that a black substance formed within the first few seconds of the reaction; this material subsequently decomposed gradually to give a lighter dark product within the following several minutes. It was proposed that an intermediate species, Fe(HS)[sup 2]-n[sub n], was formed initially from the reaction between Fe[sup 2+] and HS ions in aqueous solution and this intermediate was converted to FeS finally. The kinetic experiments showed that the rate of formation of Fe(HS)[sup 2]-n[sub n] was first order with respect to both Fe[sup 2+] and HS, with a rate constant of 103.81 (mol/l)[sup [minus]1]sec[sup [minus]1]. These results suggest that the black intermediate is FeHS[sup +].

  12. Electrochemistry: Catalysis at the boundaries

    SciTech Connect

    Appel, Aaron M.

    2014-04-09

    Renewable energy provides an opportunity to power society without the potential impacts from the use of fossil fuels, but a major limitation of sources such as solar and wind is their intermittent availability. Efficient storage of energy from these renewable sources is critical in developing their widespread utilization. One approach to the storage of renewable energy is the production of fuels, such as ethanol, from water and carbon dioxide. Unlike traditional centralized fuel production, electrochemical systems can operate under mild pressures and temperatures in dispersed, small-scale reactors. Renewable sources of energy are inherently dispersed, and therefore are well matched with the production of fuels electrochemically. However, the development of efficient catalysts is essential for the intended chemical transformations.

  13. Understanding Electrochemistry: Some Distinctive Concepts.

    ERIC Educational Resources Information Center

    Faulkner, Larry R.

    1983-01-01

    Addresses concepts about electrochemical systems that cause confusion among those new to the subject. The goal is to synthesize an understanding of the heterogeneity of an electrochemical system and a chemical sense for the important electrochemical variables of potential, current, and charge. (JN)

  14. Graphene electrochemistry: fabricating amperometric biosensors.

    PubMed

    Brownson, Dale A C; Banks, Craig E

    2011-05-21

    The electrochemical sensing of hydrogen peroxide is of substantial interest to the operation of oxidase-based amperometric biosensors. We explore the fabrication of a novel and highly sensitive electro-analytical biosensor using well characterised commercially available graphene and compare and contrast responses using Nafion -graphene and -graphite modified electrodes. Interestingly we observe that graphite exhibits a superior electrochemical response due to its enhanced percentage of edge plane sites when compared to graphene. However, when Nafion, routinely used in amperometric biosensors, is introduced onto graphene and graphite modified electrodes, re-orientation occurs in both cases which is beneficial in the former and detrimental in the latter; insights into this contrasting behaviour are consequently presented providing acuity into sensor design and development where graphene is utilised in biosensors.

  15. Applying Sociology to the Teaching of Applied Sociology.

    ERIC Educational Resources Information Center

    Wallace, Richard Cheever

    A college-level applied sociology course in which students use sociological theory or research methodology to solve social problems is described. Guidelines for determining appropriate projects are: (1) the student must feel there is a substantial need for the project; (2) the project must be approachable through recognized sociological…

  16. From art to applied science.

    PubMed

    Schatzberg, Eric

    2012-09-01

    Before "applied science" and "technology" became keywords, the concept of art was central to discourse about material culture and its connections to natural knowledge. By the late nineteenth century, a new discourse of applied science had replaced the older discourse of art. This older discourse of art, especially as presented in Enlightenment encyclopedias, addressed the relationship between art and science in depth. But during the nineteenth century the concept of fine art gradually displaced the broader meanings of "art," thus undermining the utility of the term for discourse on the relationship between knowledge and practice. This narrowed meaning of "art" obscured key aspects of the industrial world. In effect, middle-class agents of industrialism, including "men of science," used the rhetoric of "applied science" and, later, "technology" to cement the exclusion of artisanal knowledge from the discourse of industrial modernity.

  17. Women in applied behavior analysis

    PubMed Central

    McSweeney, Frances K.; Donahoe, Patricia; Swindell, Samantha

    2000-01-01

    The status of women in applied behavior analysis was examined by comparing the participation of women in the Journal of Applied Behavior Analysis (JABA) to their participation in three similar journals. For all journals, the percentage of articles with at least one female author, the percentage of authors who are female, and the percentage of articles with a female first author increased from 1978 to 1997. Participation by women in JABA was equal to or greater than participation by women in the comparison journals. However, women appeared as authors on papers in special sections of Behavior Modification substantially more often when the editor was female than when the editor was male. In addition, female membership on the editorial boards of JABA, Behavior Modification, and Behaviour Research and Therapy failed to increase from 1978 to 1997. We conclude that a “glass ceiling” reduces the participation of women at the highest levels of applied behavior analysis and related fields. PMID:22478351

  18. Applied Remote Sensing Program (ARSP)

    NASA Technical Reports Server (NTRS)

    Johnson, J. D.; Foster, K. E.; Mouat, D. A.; Miller, D. A.; Conn, J. S.

    1976-01-01

    The activities and accomplishments of the Applied Remote Sensing Program during FY 1975-1976 are reported. The principal objective of the Applied Remote Sensing Program continues to be designed projects having specific decision-making impacts as a principal goal. These projects are carried out in cooperation and collaboration with local, state and federal agencies whose responsibilities lie with planning, zoning and environmental monitoring and/or assessment in the application of remote sensing techniques. The end result of the projects is the use by the involved agencies of remote sensing techniques in problem solving.

  19. World Englishes and Applied Linguistics.

    ERIC Educational Resources Information Center

    Kachru, Braj B.

    This paper addresses the issue of the relationship between World Englishes (WE) and applied linguistics. The diffusion of English is seen in terms of three concentric circles: the Inner Circle (first-language varieties, e.g., the United States, United Kingdom), the Outer Circle (English-as-a-Second-Language varieties), and the Expanding Circle…

  20. Applied Remote Sensing Program (ARSP)

    NASA Technical Reports Server (NTRS)

    Mouat, D. A.; Johnson, J. D.; Foster, K. E.

    1977-01-01

    Descriptions of projects engaged by the Applied Remote Sensors Program in the state of Arizona are contained in an annual report for the fiscal year 1976-1977. Remote sensing techniques included thermal infrared imagery in analog and digital form and conversion of data into thermograms. Delineation of geologic areas, surveys of vegetation and inventory of resources were also presented.

  1. Applied aerodynamics: Challenges and expectations

    NASA Technical Reports Server (NTRS)

    Peterson, Victor L.; Smith, Charles A.

    1993-01-01

    Aerospace is the leading positive contributor to this country's balance of trade, derived largely from the sale of U.S. commercial aircraft around the world. This powerfully favorable economic situation is being threatened in two ways: (1) the U.S. portion of the commercial transport market is decreasing, even though the worldwide market is projected to increase substantially; and (2) expenditures are decreasing for military aircraft, which often serve as proving grounds for advanced aircraft technology. To retain a major share of the world market for commercial aircraft and continue to provide military aircraft with unsurpassed performance, the U.S. aerospace industry faces many technological challenges. The field of applied aerodynamics is necessarily a major contributor to efforts aimed at meeting these technological challenges. A number of emerging research results that will provide new opportunities for applied aerodynamicists are discussed. Some of these have great potential for maintaining the high value of contributions from applied aerodynamics in the relatively near future. Over time, however, the value of these contributions will diminish greatly unless substantial investments continue to be made in basic and applied research efforts. The focus: to increase understanding of fluid dynamic phenomena, identify new aerodynamic concepts, and provide validated advanced technology for future aircraft.

  2. Case Studies in Applied Mathematics.

    ERIC Educational Resources Information Center

    Mathematical Association of America, Washington, DC.

    This collection of nine case studies in applied mathematics was written primarily for the use of the instructor by a Conference sponsored by the Committee on the Undergraduate Program in Mathematics (CUPM). Each chapter contains exercises of varying degrees of difficulty and several include student projects. The materials were used on a trial…

  3. Applied Learning for Middle Schoolers.

    ERIC Educational Resources Information Center

    Miller, Paula; And Others

    1995-01-01

    From leading garden tours to planning a visit for Japanese teachers and participating in community theater, middle schoolers at Fort Worth's Applied Learning Academy learn academic content by working on community projects. Students' writing skills soared as they developed, edited, and field-tested brochures and trail-guide maps for their botanical…

  4. Toward an Applied Administrative Science.

    ERIC Educational Resources Information Center

    Dunbar, Roger L. M.

    1983-01-01

    A study of 65 articles from the 1981 volumes of "Administrative Science Quarterly" and "Harvard Business Review," using smallest space analysis, found that the few studies adopting subjective (instead of objective) approaches to analyzing organizational change were most likely to provide a basis for an applied administrative…

  5. Applying Creativity Research to Cooking

    ERIC Educational Resources Information Center

    Beghetto, Ronald A.; Kaufman, James C.; Hatcher, Ryan

    2016-01-01

    What, if any, benefit might there be to applying creativity research to cooking? The purpose of this paper was to address this question. Specifically, we draw on concepts and theories from creativity research to help clarify what is meant by creative cooking. This includes exploring creative cooking through the lens of the 4-C and Propulsion…

  6. Applied Linguistics Research on Asianness

    ERIC Educational Resources Information Center

    Kobayashi, Yoko

    2011-01-01

    As China is increasingly occupying the world's attention, its explosively expanding economical and political clout has also been felt in the applied linguistics domain, with the discussion on China's/Chinese language issues growing by leaps and bounds (e.g. China's English education policies, Chinese language classes in the West). Amid the world's…

  7. Influence of the substituents on the electronic and electrochemical properties of a new square-planar nickel-bis(quinoxaline-6,7-dithiolate) system: synthesis, spectroscopy, electrochemistry, crystallography, and theoretical investigation.

    PubMed

    Bolligarla, Ramababu; Reddy, Samala Nagaprasad; Durgaprasad, Gummadi; Sreenivasulu, Vudagandla; Das, Samar K

    2013-01-07

    We describe the synthesis, crystal structures, electronic absorption spectra, and electrochemistry of a series of square-planar nickel-bis(quinoxaline-6,7-dithiolate) complexes with the general formula [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)], where X = H (1a), Ph (2a), Cl (3), and Me (4). The solution and solid-state electronic absorption spectral behavior and electrochemical properties of these compounds are strongly dependent on the electron donating/accepting nature of the substituent X, attached to the quinoxaline-6,7-dithiolate ring in the system [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)]. Particularly, the charge transfer (CT) transition bands observed in the visible region are greatly affected by the electronic nature of the substituent. A possible explanation for this influence of the substituents on electronic absorption and electrochemistry is described based on highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) gaps, which is further supported by ground-state electronic structure calculations. In addition to this, the observed CT bands in all the complexes are sensitive to the solvent polarity. Interestingly, compounds 1a, 2a, 3, and 4 undergo reversible oxidation at very low oxidation potentials appearing at E(1/2) = +0.12 V, 0.033 V, 0.18 V, and 0.044 V vs Ag/AgCl, respectively, in MeOH solutions, corresponding to the respective couples [Ni(X(2)6,7-qdt)(2)](-)/[Ni(X(2)6,7-qdt)(2)](2-). Compounds 1a, 3, and 4 have been characterized unambiguously by single crystal X-ray structural analysis; compound 2a could not be characterized by single crystal X-ray structure determination because of the poor quality of the concerned crystals. Thus, we have synthesized the tetraphenyl phosphonium salt of the complex anion of 2a, [PPh(4)](2)[Ni(Ph(2)6,7-qdt)(2)]·3DMF (2b) for its structural characterization.

  8. Modeling Applied to Problem Solving

    NASA Astrophysics Data System (ADS)

    Pawl, Andrew; Barrantes, Analia; Pritchard, David E.

    2009-10-01

    Modeling Applied to Problem Solving (MAPS) is a pedagogy that helps students transfer instruction to problem solving in an expert-like manner. Declarative and Procedural syllabus content is organized and learned (not discovered) as a hierarchy of General Models. Students solve problems using an explicit Problem Modeling Rubric that begins with System, Interactions and Model (S.I.M.). System and Interactions are emphasized as the key to a strategic description of the system and the identification of the appropriate General Model to apply to the problem. We have employed the pedagogy in a three-week review course for students who received a D in mechanics. The course was assessed by a final exam retest as well as pre and post C-LASS surveys, yielding a one standard deviation improvement in the students' ability to solve final exam problems and a statistically significant positive shift in 7 of the 9 categories in the C-LASS.

  9. NIIEFA accelerators for applied purposes

    NASA Astrophysics Data System (ADS)

    Vorogushin, M. F.; Strokach, A. P.; Filatov, O. G.

    2016-12-01

    Since the foundation of the institute, we have designed and delivered more than three hundred different accelerators to Russia and abroad: cyclotrons, linear accelerators, and neutron generators. The technical characteristics of our equipment makes it competitive on the international market. Here we present the application, main parameters, and status of accelerators manufactured by NIIEFA, as well as prospects for the development of electrophysical systems for applied purposes.

  10. An Applied Physicist Does Econometrics

    NASA Astrophysics Data System (ADS)

    Taff, L. G.

    2010-02-01

    The biggest problem those attempting to understand econometric data, via modeling, have is that economics has no F = ma. Without a theoretical underpinning, econometricians have no way to build a good model to fit observations to. Physicists do, and when F = ma failed, we knew it. Still desiring to comprehend econometric data, applied economists turn to mis-applying probability theory---especially with regard to the assumptions concerning random errors---and choosing extremely simplistic analytical formulations of inter-relationships. This introduces model bias to an unknown degree. An applied physicist, used to having to match observations to a numerical or analytical model with a firm theoretical basis, modify the model, re-perform the analysis, and then know why, and when, to delete ``outliers'', is at a considerable advantage when quantitatively analyzing econometric data. I treat two cases. One is to determine the household density distribution of total assets, annual income, age, level of education, race, and marital status. Each of these ``independent'' variables is highly correlated with every other but only current annual income and level of education follow a linear relationship. The other is to discover the functional dependence of total assets on the distribution of assets: total assets has an amazingly tight power law dependence on a quadratic function of portfolio composition. Who knew? )

  11. Towards "open applied" Earth sciences

    NASA Astrophysics Data System (ADS)

    Ziegler, C. R.; Schildhauer, M.

    2014-12-01

    Concepts of open science -- in the context of cyber/digital technology and culture -- could greatly benefit applied and secondary Earth science efforts. However, international organizations (e.g., environmental agencies, conservation groups and sustainable development organizations) that are focused on applied science have been slow to incorporate open practices across the spectrum of scientific activities, from data to decisions. Myriad benefits include transparency, reproducibility, efficiency (timeliness and cost savings), stakeholder engagement, direct linkages between research and environmental outcomes, reduction in bias and corruption, improved simulation of Earth systems and improved availability of science in general. We map out where and how open science can play a role, providing next steps, with specific emphasis on applied science efforts and processes such as environmental assessment, synthesis and systematic reviews, meta-analyses, decision support and emerging cyber technologies. Disclaimer: The views expressed in this paper are those of the authors and do not necessarily reflect the views or policies of the organizations for which they work and/or represent.

  12. Trigonal-bipyramidal and square-pyramidal chromium-manganese chalcogenide clusters, [E2CrMn2(CO)n](2-) (E=S, Se, Te; n=9, 10): synthesis, electrochemistry, UV/Vis absorption, and computational studies.

    PubMed

    Shieh, Minghuey; Yu, Chun-Hsien; Chu, Yen-Yi; Guo, Yu-Wen; Huang, Chung-Yi; Hsing, Kai-Jieah; Chen, Pei-Chi; Lee, Chung-Feng

    2013-05-01

    The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr-Mn-carbonyl clusters, [E2CrMn2(CO)9](2-) (E=S, 1; Se, 2). Clusters 1 and 2 were isostructural with one another and each displayed a trigonal-bipyramidal structure, with the CrMn2 triangle axially capped by two μ3-E atoms. The analogous telluride cluster, [Te2CrMn2(CO)9](2-) (3), was obtained from the ring-closure of Te2Mn2 ring complex [Te2Mn2Cr2(CO)18](2-) (4). Upon bubbling with CO, clusters 2 and 3 were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10](2-) (E=Se, 5; Te, 6), accompanied with the cleavage of one Cr-Mn bond. According to SQUID analysis, cluster 6 was paramagnetic, with S=1 at room temperature; however, the Se analogue (5) was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster 6 could be further carbonylated, with cleavage of the Mn-Mn bond to produce a new arachno-cluster, [Te2CrMn2(CO)11](2-) (7). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations.

  13. Structural, magnetic and optical properties of an Fe(III) dimer bridged by the meridional planar divergent N,N'-bis(salicyl)hydrazide and its photo- and electro-chemistry in solution.

    PubMed

    Cheaib, Khaled; Martel, David; Clément, Nicolas; Eckes, Fabrice; Kouaho, Stéphanie; Rogez, Guillaume; Dagorne, Samuel; Kurmoo, Mohamedally; Choua, Sylvie; Welter, Richard

    2013-02-07

    {Fe(III)Cl(DMF)(2)}(2)(L) where L is N,N'-bis(salicyl)hydrazide has been synthesized as red crystals and characterized using single-crystal diffraction, infrared and UV-vis spectroscopies, and its magnetic properties studied. The dimeric unit in the structure is formed through the two meridional sets of divergent O, N, O coordinating atoms of the hexacoordinated and quadruply charged ligand. With the presence of the inversion symmetry the Fe atoms are strictly planar with the ligand. The magnetic exchange interaction is found to be antiferromagnetic with a J = -5.98(3) cm(-1) through the rare Fe-N-N-Fe pathway. Irradiation of the FeCl(3)/H(4)L red DMF solution in the visible region of the spectrum resulted in its complete discoloration and from which the unknown colorless salt [Fe(II)(DMF)(6)][Fe(II)Cl(4)] and the neutral ligand have been identified by single crystal diffraction. The UV-visible spectra of FeCl(3), H(4)L and their mixture in DMF solution indicate that the iron complex is the absorbing species and the presence of the free ligand in the irradiated solution suggests that the ligand is potentially acting as a catalyst to the photoreduction of Fe(III) to Fe(II), while electrochemistry points to a mixed-valent (Fe(II)-Fe(III)) intermediate in the process.

  14. Applying STAMP in Accident Analysis

    NASA Technical Reports Server (NTRS)

    Leveson, Nancy; Daouk, Mirna; Dulac, Nicolas; Marais, Karen

    2003-01-01

    Accident models play a critical role in accident investigation and analysis. Most traditional models are based on an underlying chain of events. These models, however, have serious limitations when used for complex, socio-technical systems. Previously, Leveson proposed a new accident model (STAMP) based on system theory. In STAMP, the basic concept is not an event but a constraint. This paper shows how STAMP can be applied to accident analysis using three different views or models of the accident process and proposes a notation for describing this process.

  15. Fire retardancy using applied materials

    NASA Technical Reports Server (NTRS)

    Feldman, R.

    1971-01-01

    An example of advanced technology transfer from the Little Joe, Surveyor, Comsat, re-entry and Apollo age to everyday fire protection needs is presented. Utilizing the principle of sublimation cooling for thermostatic temperature control, the material meets a wide range of fire retardancy and heat transmission control requirements. Properties vary from flexible tape for conduits and electrical cables to rigid coatings for column protection, with a broad spectrum of sublimation temperatures available. The material can be applied in the field or in the factory, utilizing mass production techniques, yielding a product that is reliable, effective, widely available and low in cost.

  16. Aerospace reliability applied to biomedicine.

    NASA Technical Reports Server (NTRS)

    Lalli, V. R.; Vargo, D. J.

    1972-01-01

    An analysis is presented that indicates that the reliability and quality assurance methodology selected by NASA to minimize failures in aerospace equipment can be applied directly to biomedical devices to improve hospital equipment reliability. The Space Electric Rocket Test project is used as an example of NASA application of reliability and quality assurance (R&QA) methods. By analogy a comparison is made to show how these same methods can be used in the development of transducers, instrumentation, and complex systems for use in medicine.

  17. Applying quantum principles to psychology

    NASA Astrophysics Data System (ADS)

    Busemeyer, Jerome R.; Wang, Zheng; Khrennikov, Andrei; Basieva, Irina

    2014-12-01

    This article starts out with a detailed example illustrating the utility of applying quantum probability to psychology. Then it describes several alternative mathematical methods for mapping fundamental quantum concepts (such as state preparation, measurement, state evolution) to fundamental psychological concepts (such as stimulus, response, information processing). For state preparation, we consider both pure states and densities with mixtures. For measurement, we consider projective measurements and positive operator valued measurements. The advantages and disadvantages of each method with respect to applications in psychology are discussed.

  18. Comprehensive Environmental Assessment Applied to ...

    EPA Pesticide Factsheets

    In September 2013, EPA announced the availability of the final report, Comprehensive Environmental Assessment Applied to Multiwalled Carbon Nanotube Flame-Retardant Coatings in Upholstery Textiles: A Case Study Presenting Priority Research Gaps for Future Risk Assessments. This final report presents a case study of multiwalled carbon nanotubes (MWCNTs); it focuses on the specific example of MWCNTs as used in flame-retardant coatings applied to upholstery textiles. This case study is organized around the comprehensive environmental assessment (CEA) framework, which structures available information pertaining to the product life cycle, environmental transport and fate, exposure-dose in receptors (i.e., humans, ecological populations, and the environment), and potential impacts in these receptors. A group of experts representing multiple disciplines and multiple sector perspectives used an earlier draft of the case study in conjunction with a structured workshop process to identify and prioritize research gaps that, if pursued, could inform future MWCNT assessment efforts. The final report is not a health, risk, or exposure assessment and as such does not draw conclusions about potential risks, or present an exhaustive review of the literature. Rather, it presents the MWCNT research priorities that experts identified in this application of CEA in order to aid research planning throughout the scientific community. The outcomes of these research efforts may subsequ

  19. Implementing an Applied Science Program

    NASA Technical Reports Server (NTRS)

    Rickman, Doug; Presson, Joan

    2007-01-01

    The work implied in the NASA Applied Science Program requires a delicate balancing act for the those doing it. At the implementation level there are multiple tensions intrinsic to the program. For example each application of an existing product to a decision support process requires deep knowledge about the data and deep knowledge about the decision making process. It is highly probable no one person has this range of knowledge. Otherwise the decision making process would already be using the data. Therefore, a team is required. But building a team usually requires time, especially across agencies. Yet the program mandates efforts of relatively short duration. Further, those who know the data are scientists, which makes them essential to the program. But scientists are evaluated on their publication record. Anything which diverts a scientist from the research for his next publication is an anathema to him and potential death to their career. Trying to get another agency to use NASA data does not strike most scientists as material inherently suitable for publication. Also, NASA wishes to rapidly implement often substantial changes to another agency's process. For many reasons, such as budget and program constraints, speed is important. But the owner of a decision making process is tightly constrained, usually by law, regulation, organization and custom. Changes when made are slow, cautious, even hesitant, and always done according a process specific to the situation. To manage this work MSFC must balance these and other tensions. Some things we have relatively little control over, such as budget. These we try to handle by structural techniques. For example by insisting all of our people work on multiple projects simultaneously we inherently have diversification of funding for all of our people. In many cases we explicitly use some elements of tension to be productive. For example the need for the scientists to constantly publish is motivation to keep tasks short and

  20. Applied public-key steganography

    NASA Astrophysics Data System (ADS)

    Guillon, Pierre; Furon, Teddy; Duhamel, Pierre

    2002-04-01

    We consider the problem of hiding information in a steganographic framework, i.e. embedding a binary message within an apparently innocuous content, in order to establish a suspicion-free digital communication channel. The adversary is passive as no intentional attack is foreseen. The only threat is that she discovers the presence of a hidden communication. The main goal of this article is to find if the Scalar Costa Scheme, a recently published embedding method exploiting side information at the encoder, is suitable for that framework. We justify its use assessing its security level with respect to the Cachin's criterion. We derive a public-key stego-system following the ideas of R. Anderson and P. Petitcolas. This technique is eventually applied to PCM audio contents. Experimental performances are detailed in terms of bit-rate and Kullback-Leibler distance.

  1. Data Understanding Applied to Optimization

    NASA Technical Reports Server (NTRS)

    Buntine, Wray; Shilman, Michael

    1998-01-01

    The goal of this research is to explore and develop software for supporting visualization and data analysis of search and optimization. Optimization is an ever-present problem in science. The theory of NP-completeness implies that the problems can only be resolved by increasingly smarter problem specific knowledge, possibly for use in some general purpose algorithms. Visualization and data analysis offers an opportunity to accelerate our understanding of key computational bottlenecks in optimization and to automatically tune aspects of the computation for specific problems. We will prototype systems to demonstrate how data understanding can be successfully applied to problems characteristic of NASA's key science optimization tasks, such as central tasks for parallel processing, spacecraft scheduling, and data transmission from a remote satellite.

  2. Modeling Applied to Problem Solving

    NASA Astrophysics Data System (ADS)

    Pawl, Andrew; Barrantes, Analia; Pritchard, David E.

    2009-11-01

    We describe a modeling approach to help students learn expert problem solving. Models are used to present and hierarchically organize the syllabus content and apply it to problem solving, but students do not develop and validate their own Models through guided discovery. Instead, students classify problems under the appropriate instructor-generated Model by selecting a system to consider and describing the interactions that are relevant to that system. We believe that this explicit System, Interactions and Model (S.I.M.) problem modeling strategy represents a key simplification and clarification of the widely disseminated modeling approach originated by Hestenes and collaborators. Our narrower focus allows modeling physics to be integrated into (as opposed to replacing) a typical introductory college mechanics course, while preserving the emphasis on understanding systems and interactions that is the essence of modeling. We have employed the approach in a three-week review course for MIT freshmen who received a D in the fall mechanics course with very encouraging results.

  3. Data compression applied to HHVT

    NASA Technical Reports Server (NTRS)

    Thompson, William K.

    1990-01-01

    A task order was written by the High Resolution, High Frame Rate Video Technology (HHVT) project engineers to study data compression techniques that could be applied to the HHVT system. Specifically, the goals of the HHVT data compression study are to accomplish the following: (1) Determine the downlink capabilities of the Space Shuttle and Space Station Freedom to support HHVT data (i.e., determine the maximum data rates and link availability); (2) Determine current and projected capabilities of high speed storage media to support HHVT data by determining their maximum data acquisition/transmission rates and volumes; (3) Identify which experiment in the HHVT Users' Requirement data base need data compression, based on the experiments' imaging requirements; (4) Select the best data compression technique for each of these users by identifying a technique that provides compression but minimizes distortion; and (5) Investigate state-of-the-art technologies for possible implementation of selected data compression techniques. Data compression will be needed because of the high data rates and larger volumes of data that will result from the use of digitized video onboard the Space Shuttle and Space Station Freedom.

  4. Intelligence Applied to Air Vehicles

    NASA Technical Reports Server (NTRS)

    Rosen, Robert; Gross, Anthony R.; Fletcher, L. Skip; Zornetzer, Steven (Technical Monitor)

    2000-01-01

    The exponential growth in information technology has provided the potential for air vehicle capabilities that were previously unavailable to mission and vehicle designers. The increasing capabilities of computer hardware and software, including new developments such as neural networks, provide a new balance of work between humans and machines. This paper will describe several NASA projects, and review results and conclusions from ground and flight investigations where vehicle intelligence was developed and applied to aeronautical and space systems. In the first example, flight results from a neural network flight control demonstration will be reviewed. Using, a highly-modified F-15 aircraft, a NASA/Dryden experimental flight test program has demonstrated how the neural network software can correctly identify and respond to changes in aircraft stability and control characteristics. Using its on-line learning capability, the neural net software would identify that something in the vehicle has changed, then reconfigure the flight control computer system to adapt to those changes. The results of the Remote Agent software project will be presented. This capability will reduce the cost of future spacecraft operations as computers become "thinking" partners along with humans. In addition, the paper will describe the objectives and plans for the autonomous airplane program and the autonomous rotorcraft project. Technologies will also be developed.

  5. A Multiple Approach to Evaluating Applied Academics.

    ERIC Educational Resources Information Center

    Wang, Changhua; Owens, Thomas

    The Boeing Company is involved in partnerships with Washington state schools in the area of applied academics. Over the past 3 years, Boeing offered grants to 57 high schools to implement applied mathematics, applied communication, and principles of technology courses. Part 1 of this paper gives an overview of applied academics by examining what…

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

    PubMed

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

    2014-07-28

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

  7. Morphometrics applied to medical entomology.

    PubMed

    Dujardin, Jean-Pierre

    2008-12-01

    Morphometrics underwent a revolution more than one decade ago. In the modern morphometrics, the estimate of size is now contained in a single variable reflecting variation in many directions, as many as there are landmarks under study, and shape is defined as their relative positions after correcting for size, position and orientation. With these informative data, and the corresponding software freely available to conduct complex analyses, significant biological and epidemiological features can be quantified more accurately. We discuss the evolutionary significance of the environmental impact on metric variability, mentioning the importance of concepts like genetic assimilation, genetic accommodation, and epigenetics. We provide examples of measuring the effect of selection on metric variation by comparing (unpublished) Qst values with corresponding (published) Fst. The primary needs of medical entomologists are to distinguish species, especially cryptic species, and to detect them where they are not expected. We explain how geometric morphometrics could apply to these questions, and where there are deficiencies preventing the approach from being utilized at its maximum potential. Medical entomologists in connection with control programs aim to identify isolated populations where the risk of reinfestation after treatment would be low ("biogeographical islands"). Identifying them can be obtained from estimating the number of migrants per generation. Direct assessment of movement remains the most valid approach, but it scores active movement only. Genetic methods estimating gene flow levels among interbreeding populations are commonly used, but gene flow does not necessarily mean the current flow of migrants. Methods using the morphometric variation are neither suited to evaluate gene flow, nor are they adapted to estimate the flow of migrants. They may provide, however, the information needed to create a preliminary map pointing to relevant areas where one could

  8. Data Assimilation for Applied Meteorology

    NASA Astrophysics Data System (ADS)

    Haupt, S. E.

    2012-12-01

    Although atmospheric models provide a best estimate of the future state of the atmosphere, due to sensitivity to initial condition, it is difficult to predict the precise future state. For applied problems, however, users often depend on having accurate knowledge of that future state. To improve prediction of a particular realization of an evolving flow field requires knowledge of the current state of that field and assimilation of local observations into the model. This talk will consider how dynamic assimilation can help address the concerns of users of atmospheric forecasts. First, we will look at the value of assimilation for the renewable energy industry. If the industry decision makers can have confidence in the wind and solar power forecasts, they can build their power allocations around the expected renewable resource, saving money for the ratepayers as well as reducing carbon emissions. We will assess the value to that industry of assimilating local real-time observations into the model forecasts and the value that is provided. The value of the forecasts with assimilation is important on both short (several hour) to medium range (within two days). A second application will be atmospheric transport and dispersion problems. In particular, we will look at assimilation of concentration data into a prediction model. An interesting aspect of this problem is that the dynamics are a one-way coupled system, with the fluid dynamic equations affecting the concentration equation, but not vice versa. So when the observations are of the concentration, one must infer the fluid dynamics. This one-way coupled system presents a challenge: one must first infer the changes in the flow field from observations of the contaminant, then assimilate that to recover both the advecting flow and information on the subgrid processes that provide the mixing. To accomplish such assimilation requires a robust method to match the observed contaminant field to that modeled. One approach is

  9. Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry

    DOE PAGES

    Gul, Sheraz; Ng, Jia Wei Desmond; Alonso-Mori, Roberto; ...

    2015-02-25

    Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based onmore » the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. In conclusion, the detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.« less

  10. Simultaneous Detection of Electronic Structure Changes from Two Elements of a Bifunctional Catalyst Using Wavelength-Dispersive X-ray Emission Spectroscopy and in situ Electrochemistry

    PubMed Central

    Gul, Sheraz; Desmond Ng, Jia Wei; Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis; Anzenberg, Eitan; Lassalle-Kaiser, Benedikt; Gorlin, Yelena; Weng, Tsu-Chien; Zwart, Petrus H.; Zhang, Jin Z.; Bergmann, Uwe; Yachandra, Vittal K.; Jaramillo, Thomas F.; Yano, Junko

    2015-01-01

    Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based on the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. The detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions. PMID:25747045

  11. Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry

    SciTech Connect

    Gul, Sheraz; Ng, Jia Wei Desmond; Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis; Anzenberg, Eitan; Lassalle-Kaiser, Benedikt; Gorlin, Yelena; Weng, Tsu-Chien; Zwart, Petrus H.; Zhang, Jin Z.; Bergmann, Uwe; Yachandra, Vittal K.; Jaramillo, Thomas F.; Yano, Junko

    2015-02-25

    Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based on the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. In conclusion, the detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.

  12. Applied Psycholinguistics--Amphibian or Phantom?

    ERIC Educational Resources Information Center

    Titone, Renzo

    1975-01-01

    A tentative classification of internal departments of psycholinguistics is suggested and a list of applied fields is presented. Applied psycholinguistics is not seen here to have a right to scientific independence. (SCC)

  13. Western Perspectives in Applied Linguistics in Africa

    ERIC Educational Resources Information Center

    Makoni, Sinfree; Meinhof, Ulrike H.

    2004-01-01

    The aim of this article is to analyze the nature of the historical and contemporary social contexts within which applied linguistics in Africa emerged, and is currently practiced. The article examines the challenges "local" applied Linguistics in Africa is confronted with as it tries to amplify applied linguistic programs emanating from…

  14. Critical and Alternative Directions in Applied Linguistics

    ERIC Educational Resources Information Center

    Pennycook, Alastair

    2010-01-01

    Critical directions in applied linguistics can be understood in various ways. The term "critical" as it has been used in "critical applied linguistics," "critical discourse analysis," "critical literacy" and so forth, is now embedded as part of applied linguistic work, adding an overt focus on questions of power and inequality to discourse…

  15. An Efficient CuxO Photocathode for Hydrogen Production at Neutral pH: New Insights from Combined Spectroscopy and Electrochemistry.

    PubMed

    Baran, Tomasz; Wojtyła, Szymon; Lenardi, Cristina; Vertova, Alberto; Ghigna, Paolo; Achilli, Elisabetta; Fracchia, Martina; Rondinini, Sandra; Minguzzi, Alessandro

    2016-08-24

    Light-driven water splitting is one of the most promising approaches for using solar energy in light of more sustainable development. In this paper, a highly efficient p-type copper(II) oxide photocathode is studied. The material, prepared by thermal treatment of CuI nanoparticles, is initially partially reduced upon working conditions and soon reaches a stable form. Upon visible-light illumination, the material yields a photocurrent of 1.3 mA cm(-2) at a potential of 0.2 V vs a reversible hydrogen electrode at mild pH under illumination by AM 1.5 G and retains 30% of its photoactivity after 6 h. This represents an unprecedented result for a nonprotected Cu oxide photocathode at neutral pH. The photocurrent efficiency as a function of the applied potential was determined using scanning electrochemical microscopy. The material was characterized in terms of photoelectrochemical features; X-ray photoelectron spectroscopy, X-ray absorption near-edge structure, fixed-energy X-ray absorption voltammetry, and extended X-ray absorption fine structure analyses were carried out on pristine and used samples, which were used to explain the photoelectrochemical behavior. The optical features of the oxide are evidenced by direct reflectance spectroscopy and fluorescence spectroscopy, and Mott-Schottky analysis at different pH values explains the exceptional activity at neutral pH.

  16. Ice crystals growth driving assembly of porous nitrogen-doped graphene for catalyzing oxygen reduction probed by in situ fluorescence electrochemistry

    PubMed Central

    Wang, Jiong; Wang, Huai-Song; Wang, Kang; Wang, Feng-Bin; Xia, Xing-Hua

    2014-01-01

    In recent years, doped carbonaceous materials as alternative catalysts for oxygen reduction reaction (ORR) have received considerable attention due to the low cost and high CO tolerance capability. Different theoretical studies have suggested that oxygen is reduced in a rapid sequence intermediated by diverse oxygen-containing reactive intermediates (ORI). However, due to the short lifetimes of the possible ORI, direct experimental evidence is very difficult to be obtained. Here, we report the synthesis of an ultralight and porous nitrogen-doped graphene (NG) by annealing graphite oxide (GO)-melamine scaffold shaped in ice template. The resultant NG exhibits excellent electrocatalytic activity toward 4e-reduction of oxygen with the onset potential as low as −0.05 V vs. Ag/AgCl in alkaline media. Using this material as model study, sensitive in situ fluorescence spectroelectrochemistry is applied to demonstrate the presence the reactive ORI. The global ORR pathway is unraveled as stepwise electron transfer involving hydroxyl radical as the important intermediate via both inner- and outer-sphere process. This result would likely provide a new insight into the further understanding of ORR mechanism on those intrinsic carbonaceous materials. PMID:25335571

  17. Fabrication of bulk-modified carbon paste electrode containing alpha-PW12O40(3-) polyanion supported on modified silica gel: Preparation, electrochemistry and electrocatalysis.

    PubMed

    Hamidi, Hassan; Shams, Esmaeil; Yadollahi, Bahram; Esfahani, Farhad Kabiri

    2008-01-15

    Alpha-PW(12)O(40)(3-) (PW(12)) supported on the surface of silica gel derivatized by 3-aminopropyl(triethoxy)silane (devoted briefly as SiNH(3)PW(12)) was synthesized and used as bulk modifier to fabricate a renewable three-dimensional chemically modified electrode. The electrochemical behavior of the modified electrode was characterized by cyclic voltammetry. There is an ionic bonding character between PW(12) and the surface amino groups of modified silica, which greatly improves the stability of SiNH(3)PW(12)-modified carbon paste electrode due to insolubility of silica gel in water. The SiNH(3)PW(12) bulk-modified carbon paste electrode not only maintains the electrochemical activity of PW(12), but also exhibits remarkable advantages of renewability, as well as simple preparation and inexpensive material. The modified electrode offers an excellent and stable electrocatalytic response for the reduction of IO(3)(-) and hydrogen peroxide. The SiNH(3)PW(12)-CPE is successfully applied as an electrochemical detector to monitor IO(3)(-) in flow injection analysis (FIA). The catalytic peak current was found to be linear with the IO(3)(-) concentration in the range 5x10(-6) to 1x10(-3)molL(-1). The detection limit of the proposed method was found to be 3.1x10(-6)molL(-1) for IO(3)(-) determination.

  18. Investigation of the electrode kinetics and electrochemistry of refractory-metal deposition. Final report, 26 April 1982-30 June 1985

    SciTech Connect

    White, S.H.; Twardoch, U.M.

    1986-07-01

    Electrochemical methods represent important ways in which the refractory-metal coatings can be applied to the more active metals and alloys to take advantage, at the new surface, of their superior properties to provide erosion and corrosion protection. Currently, of the refractory metals, only chromium can be plated from aqueous solution, albeit in a form that is not entirely free of cracks and pores. These aberrations in the coating can lead to protection failure under severe conditions. The remaining metals can be plated from molten fluoride electrolytes at temperatures in excess of 700 C. It is clear that less-severe operating conditions are required for the plating of these metals, to take advantage of their properties in coatings upon as wide a range of materials as possible. The plating process involves the transport of ionic species, established in an ionic medium, to the solution electrode interface at which these species undergo electron transfer reactions and ligand removal to form metal atoms at favored sites. The aggregation of these atoms into clusters of nuclei, their growth into crystallites, and the accumulation of crystallites into a coherent polycrystalline metal coating, represents the final stages of the complex process of metal plating. This program of work has explored some aspects of each of these contributing processes to develop a scientific basis for the design of new plating baths and techniques which can be operated for chromium and molybdenum at substantially lower temperatures.

  19. Fast and simultaneous detection of heavy metals using a simple and reliable microchip-electrochemistry route: An alternative approach to food analysis.

    PubMed

    Chailapakul, Orawon; Korsrisakul, Sarawadee; Siangproh, Weena; Grudpan, Kate

    2008-01-15

    This paper reports, for the first, the fast and simultaneous detection of prominent heavy metals, including: lead, cadmium and copper using microchip CE with electrochemical detection. The direct amperometric detection mode for microchip CE was successfully applied to these heavy metal ions. The influences of separation voltage, detection potential, as well as the concentration and pH value of the running buffer on the response of the detector were carefully assayed and optimized. The results clearly show that reliable analysis for lead, cadmium, and copper by the degree of electrophoretic separation occurs in less than 3min using a MES buffer (pH 7.0, 25mM) and l-histidine, with 1.2kV separation voltage and -0.8V detection potential. The detection limits for Pb(2+), Cd(2+), and Cu(2+) were 1.74, 0.73 and 0.13microM (S/N=3). The %R.S.D. of each peak current was <6% and migration times <2% for prolonged operation. To demonstrate the potential and future role of microchip CE, analytical possibilities and a new route in the raw sample analysis were presented. The results obtained allow the proposed microchip CE-ED acts as an alternative approach for metal analysis in foods.

  20. Ferrocenoyl piperazide as derivatizing agent for the analysis of isocyanates and related compounds using liquid chromatography/electrochemistry/mass spectrometry (LC/EC/MS).

    PubMed

    Seiwert, Bettina; Henneken, Hartmut; Karst, Uwe

    2004-12-01

    Ferrocenoyl piperazide is introduced as a new pre-column derivatizing agent for the analysis of various isocyanates in air samples using reversed-phase liquid chromatographic separation, electrochemical oxidation/ionization, and mass spectrometry. The nonpolar derivatives can be separated well using a phenyl-modified stationary phase and a formic acid/ammonium formate buffer of pH 3, which yields excellent separations, especially for one problematic group of isocyanates consisting of 2,4- and 2,6-toluylenediisocyanate (2,4- and 2,6-TDI) and hexamethylenediisocyanate (HDI). Electrochemical oxidation at low potentials (0.5 V versus Pd/H(2)) leads to formation of charged products, which are nebulized in a commercial atmospheric pressure chemical ionization (APCI) source, with the corona discharge operated only at low voltage. Limits of detection between 6 and 20 nmol/L are obtained for the isocyanate derivatives, and calibration is linear over at least two decades of concentration. The method is applied for the analysis of air after thermal degradation of a polyurethane foam, and it is demonstrated that it is suitable as well for the analysis of carboxylic acid chlorides and of isothiocyanates.

  1. Towards understanding surface chemistry and electrochemistry of La0.1Sr0.9TiO3-α based solid oxide fuel cell anodes

    NASA Astrophysics Data System (ADS)

    Yurkiv, Vitaliy; Constantin, Guillaume; Hornes, Aitor; Gondolini, Angela; Mercadelli, Elisa; Sanson, Alessandra; Dessemond, Laurent; Costa, Rémi

    2015-08-01

    In the present contribution, we combine modeling and experimental study of electrochemical hydrogen oxidation at an alternative perovskite based mixed-conducting SOFC anode. Composite electrodes were produced by conventional wet ceramic processing (screen printing - spraying) and sintering on YSZ electrolytes (La0.1Sr0.9TiO3-α-Ce1-xGdxO2-α|YSZ) with different compositions and microstructure, and were electrochemically characterized using symmetrical button-cells configuration. An elementary kinetic model was developed and applied to explore the performance of LST based SOFC anode. A detailed multi-step heterogeneous chemical and electrochemical reaction mechanism was established taking into account transport of ions in all ionic phases, and gas transport in channel and porous media. It was found that heterogeneous chemistry at LST surface has capacitive behavior that alters the impedance spectra. In addition, surface charge-transfer reaction, which describes partial oxygen ionization, caused impedance feature and is rate-limiting at high temperature. The gas transport in the supply chamber (gas conversion) is significant only at moderate temperatures.

  2. Combination of electrochemistry with chemometrics to introduce an efficient analytical method for simultaneous quantification of five opium alkaloids in complex matrices.

    PubMed

    Gholivand, Mohammad-Bagher; Jalalvand, Ali R; Goicoechea, Hector C; Gargallo, Raimundo; Skov, Thomas; Paimard, Giti

    2015-01-01

    For the first time, an analytical methodology based on differential pulse voltammetry (DPV) at a glassy carbon electrode (GCE) and integration of three efficient strategies including variable selection based on ant colony optimization (ACO), mathematical pre-processing selection by genetic algorithm (GA), and sample selection (SS) through a distance-based procedure to improve partial least squares-1 (PLS-1, ACO-GA-SS-PLS-1) multivariate calibration (MVC) for the simultaneous determination of five opium alkaloids including morphine (MOP), noscapine (NOP), thebaine (TEB), codeine (COD), and papaverine (PAP) was used and validated. The baselines of the DPV signals were modeled as a smooth curve, using P-splines, a combination of B-splines and a discrete roughness penalty. After subtraction of the baseline we got a signal with a two-component probability density. One component was for the peaks and it was approximated by a uniform distribution on the potential axis. The other component was for the observed noise around the baseline. Some sources of bi-linearity deviation for electrochemical data were discussed and analyzed. The lack of bi-linearity was tackled by potential shift correction using correlation optimized warping (COW) algorithm. The MVC model was developed as a quinternary calibration model in a blank human serum sample (drug-free) provided by a healthy volunteer to regard the presence of a strong matrix effect which may be caused by the possible interferents present in the serum, and it was validated and tested with two independent sets of analytes mixtures in the blank and actual human serum samples, respectively. Fortunately, the proposed methodology was successful in simultaneous determination of MOP, NOP, TEB, COD, and PAP in both blank and actual human serum samples and its results were satisfactory comparable to those obtained by applying the reference method based on high performance liquid chromatography-ultraviolet detection (HPLC-UV).

  3. Electrochemistry of chemically lithiated NaV{sub 3}O{sub 8}: A positive electrode material for use in rechargeable lithium-ion batteries

    SciTech Connect

    Spahr, M.E. |; Novak, P.; Scheifele, W.; Haas, O.; Nesper, R.

    1998-02-01

    Monoclinic NaV{sub 3}O{sub 8} was prepared via aqueous precipitation and subsequently chemically lithiated using butyllithium in hexane as lithiation reagent. The topochemical lithiation process leads to materials with variable lithium content depending on the lithiation reaction conditions. Up to 3 Li{sup +}/mol could be inserted chemically in the lattice water-free NaV{sub 3}O{sub 8} and result in cleavage of the particles, which leads to highly dispersed materials. In contrast to the chemical insertion method, almost 3.5 Li{sup +}/mol could be electrochemically inserted in NaV{sub 3}O{sub 8}, corresponding to a specific charge of about 310 mAh/g. About 2.5 Li{sup +}/mol could be deinserted potentiodynamically in the potential range from 1.5 to 4.0 V vs Li/Li{sup +} from a chemically lithiated material with the composition Li{sub 3}NaV{sub 3}O{sub 8}. This corresponds to a specific charge of about 215 mAh/g. In galvanostatic cycling experiments, a specific charge of more than 200 mAh/g could be demonstrated for 100 cycles using this electrode material. The specific charges obtained are independent of the applied specific current up to 50 mA/g of the oxide. This behavior indicates that the sodium vanadate host material can support high lithium insertion and deinsertion rates, which make the chemically lithiated form an attractive candidate for lithium-containing positive electrode materials in high-power lithium-ion batteries.

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

    PubMed Central

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

    2013-01-01

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

  5. Comparative study of the oxidation behavior of sulfur-containing amino acids and glutathione by electrochemistry-mass spectrometry in the presence and absence of cisplatin.

    PubMed

    Zabel, Robert; Weber, Günther

    2016-02-01

    Small sulfur-containing compounds are involved in several important biochemical processes, including-but not limited to-redox regulation and drug conjugation/detoxification. While methods for stable redox pairs of such compounds (thiols/disulfides) are available, analytical data on more labile and short-lived redox intermediates are scarce, due to highly challenging analytical requirements. In this study, we employ the direct combination of reagentless electrochemical oxidation and mass spectrometric (EC-MS) identification for monitoring oxidation reactions of cysteine, N-acetylcysteine, methionine, and glutathione under simulated physiological conditions (pH 7.4, 37 °C). For the first time, all theoretically expected redox intermediates-with only one exception-are detected simultaneously and in situ, including sulfenic, sulfinic, and sulfonic acids, disulfides, thiosulfinates, thiosulfonates, and sulfoxides. By monitoring the time/potential-dependent interconversion of sulfur species, mechanistic oxidation routes are confirmed and new reactions detected, e.g., sulfenamide formation due to reaction with ammonia from the buffer. Furthermore, our results demonstrate a highly significant impact of cisplatin on the redox reactivity of sulfur species. Namely, the amount of thiol oxidation to sulfonic acid via sulfenic and sulfinic acid intermediates is diminished for glutathione in the presence of cisplatin in favor of the disulfide formation, while for N-acetylcysteine the contrary applies. N-acetylcysteine is the only ligand which displays enhanced oxidation currents upon cisplatin addition, accompanied by increased levels of thiosulfinate and thiosulfonate species. This is traced back to thiol reactivity and highlights the important role of sulfenic acid intermediates, which may function as a switch between different oxidation routes.

  6. Neural Networks Applied to Signal Processing

    DTIC Science & Technology

    1989-09-01

    DTIC FILE COpy NAVAL POSTGRADUATE SCHOOL . Monterey, California Lf 0 (0 V’ STATES 4 THESIS NEURAL NETWORKS APPLIED TO SIGNAL PROCESSING by Mark D...FUNDING NUMBERS PROGRAM PROJECT TASK WORK UNIT ELEMENT NO NO NO ACCESSION NO. 11. TITLE (Include Security Classification) NEURAL NETWORKS APPLIED TO...for public release; distribution is unlimited Neural Networks Applied to Signal Processing by Mark D. Baehre Captain, United States Army B.S., United

  7. The Contextual Interference Effect in Applied Settings

    ERIC Educational Resources Information Center

    Barreiros, Joao; Figueiredo, Teresa; Godinho, Mario

    2007-01-01

    This paper analyses the research literature that approaches the contextual interference effect in applied settings. In contrast to the laboratory settings, in which high interference conditions depress acquisition and promote learning evaluated in retention and transfer tests, in applied settings most of the studies (60%) fail to observe positive…

  8. Applied Linguistics in Its Disciplinary Context

    ERIC Educational Resources Information Center

    Liddicoat, Anthony J.

    2010-01-01

    Australia's current attempt to develop a process to evaluate the quality of research (Excellence in Research for Australia--ERA) places a central emphasis on the disciplinary organisation of academic work. This disciplinary focus poses particular problems for Applied Linguistics in Australia. This paper will examine Applied Linguistics in relation…

  9. Autobiographic Narratives as Data in Applied Linguistics

    ERIC Educational Resources Information Center

    Pavlenko, Aneta

    2007-01-01

    In the past decade, language memoirs, linguistic autobiographies, and learners' journals and diaries have become a popular means of data collection in applied linguistics. It is not always clear however how one should go about analyzing these data. The aim of this paper is to offer a critical review of analytical frameworks applied to second…

  10. Applied Behavior Analysis and Statistical Process Control?

    ERIC Educational Resources Information Center

    Hopkins, B. L.

    1995-01-01

    Incorporating statistical process control (SPC) methods into applied behavior analysis is discussed. It is claimed that SPC methods would likely reduce applied behavior analysts' intimate contacts with problems and would likely yield poor treatment and research decisions. Cases and data presented by Pfadt and Wheeler (1995) are cited as examples.…

  11. Why They Didn't Apply.

    ERIC Educational Resources Information Center

    Baker, Michael E.; Meganathan, Ami

    Prospective students who received application materials for Carnegie-Mellon University (CMU), Pennsylvania, in 1976 and 1978 but did not apply for admission were surveyed to determine student background factors or attitudes that may have influenced their choice of colleges to which they applied. Findings include the following: nonapplicants…

  12. Applied Implications of Reinforcement History Effects

    ERIC Educational Resources Information Center

    Pipkin, Claire St. Peter; Vollmer, Timothy R.

    2009-01-01

    Although the influence of reinforcement history is a theoretical focus of behavior analysis, the specific behavioral effects of reinforcement history have received relatively little attention in applied research and practice. We examined the potential effects of reinforcement history by reviewing nonhuman, human operant, and applied research and…

  13. 32 CFR 37.1220 - Applied research.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... REGULATIONS TECHNOLOGY INVESTMENT AGREEMENTS Definitions of Terms Used in This Part § 37.1220 Applied research... technology such as new materials, devices, methods and processes. It typically is funded in Research... 32 National Defense 1 2013-07-01 2013-07-01 false Applied research. 37.1220 Section...

  14. 32 CFR 37.1220 - Applied research.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... REGULATIONS TECHNOLOGY INVESTMENT AGREEMENTS Definitions of Terms Used in This Part § 37.1220 Applied research... technology such as new materials, devices, methods and processes. It typically is funded in Research... 32 National Defense 1 2010-07-01 2010-07-01 false Applied research. 37.1220 Section...

  15. 32 CFR 37.1220 - Applied research.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... REGULATIONS TECHNOLOGY INVESTMENT AGREEMENTS Definitions of Terms Used in This Part § 37.1220 Applied research... technology such as new materials, devices, methods and processes. It typically is funded in Research... 32 National Defense 1 2011-07-01 2011-07-01 false Applied research. 37.1220 Section...

  16. Nuclear Facilities and Applied Technologies at Sandia

    SciTech Connect

    Wheeler, Dave; Kaiser, Krista; Martin, Lonnie; Hanson, Don; Harms, Gary; Quirk, Tom

    2014-11-28

    The Nuclear Facilities and Applied Technologies organization at Sandia National Laboratories’ Technical Area Five (TA-V) is the leader in advancing nuclear technologies through applied radiation science and unique nuclear environments. This video describes the organization’s capabilities, facilities, and culture.

  17. Applying Information Competency to Digital Reference.

    ERIC Educational Resources Information Center

    Ellis, Lisa; Francoeur, Stephen

    This paper presents a case for applying information competency (IC) standards to digital reference services at academic libraries. Practical reasons for applying standards or guidelines to e-mail and online chat reference services are given with some insight to the nature of digital reference interactions. The standards that arose from the…

  18. Applying Psychological Theories to Educational Practice

    ERIC Educational Resources Information Center

    Sternberg, Robert

    2008-01-01

    Two approaches to the application of psychological theories to education might be referred to as domain-general and domain-specific. The domain-general approach seeks a general theory of cognitive and other skills that apply across subject-matter areas. The domain-specific approach seeks to apply specific theories within given domains, such as…

  19. Applied Linguistics: The Challenge of Theory

    ERIC Educational Resources Information Center

    McNamara, Tim

    2015-01-01

    Language has featured prominently in contemporary social theory, but the relevance of this fact to the concerns of Applied Linguistics, with its necessary orientation to practical issues of language in context, represents an ongoing challenge. This article supports the need for a greater engagement with theory in Applied Linguistics. It considers…

  20. Applied Mathematics Should Be Taught Mixed.

    ERIC Educational Resources Information Center

    Brown, Gary I.

    1994-01-01

    Discusses the differences between applied and pure mathematics and provides extensive history of mixed mathematics. Argues that applied mathematics should be taught allowing for speculative mathematics, which involves breaking down a given problem into simpler parts until one arrives at first principles. (ASK)

  1. 32 CFR 37.1220 - Applied research.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 32 National Defense 1 2014-07-01 2014-07-01 false Applied research. 37.1220 Section 37.1220... REGULATIONS TECHNOLOGY INVESTMENT AGREEMENTS Definitions of Terms Used in This Part § 37.1220 Applied research... technology such as new materials, devices, methods and processes. It typically is funded in...

  2. 32 CFR 37.1220 - Applied research.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 32 National Defense 1 2012-07-01 2012-07-01 false Applied research. 37.1220 Section 37.1220... REGULATIONS TECHNOLOGY INVESTMENT AGREEMENTS Definitions of Terms Used in This Part § 37.1220 Applied research... technology such as new materials, devices, methods and processes. It typically is funded in...

  3. Child Participant Roles in Applied Linguistics Research

    ERIC Educational Resources Information Center

    Pinter, Annamaria

    2014-01-01

    Children's status as research participants in applied linguistics has been largely overlooked even though unique methodological and ethical concerns arise in projects where children, rather than adults, are involved. This article examines the role of children as research participants in applied linguistics and discusses the limitations of…

  4. The basic importance of applied behavior analysis

    PubMed Central

    Epling, W. Frank; Pierce, W. David

    1986-01-01

    We argue that applied behavior analysis is relevant to basic research. Modification studies, and a broad range of investigations that focus on the precipitating and maintaining conditions of socially significant human behavior, have basic importance. Applied behavior analysis may aid basic researchers in the design of externally valid experiments and thereby enhance the theoretical significance of basic research for understanding human behavior. Applied research with humans, directed at culturally-important problems, will help to propagate the science of human behavior. Such a science will also be furthered by analogue experiments that model socially important behavior. Analytical-applied studies and analogue experiments are forms of applied behavior analysis that could suggest new environment-behavior relationships. These relationships could lead to basic research and principles that further the prediction, control, and understanding of behavior. PMID:22478650

  5. History and theory in "applied ethics".

    PubMed

    Beauchamp, Tom L

    2007-03-01

    Robert Baker and Laurence McCullough argue that the "applied ethics model" is deficient and in need of a replacement model. However, they supply no clear meaning to "applied ethics" and miss most of what is important in the literature on methodology that treats this question. The Baker-McCullough account of medical and applied ethics is a straw man that has had no influence in these fields or in philosophical ethics. The authors are also on shaky historical grounds in dealing with two problems: (1) the historical source of the notion of "practical ethics" and (2) the historical source of and the assimilation of the term "autonomy" into applied philosophy and professional ethics. They mistakenly hold (1) that the expression "practical ethics" was first used in a publication by Thomas Percival and (2) that Kant is the primary historical source of the notion of autonomy as that notion is used in contemporary applied ethics.

  6. Applied Aeroscience and CFD Branch Overview

    NASA Technical Reports Server (NTRS)

    LeBeau, Gerald J.; Kirk, Benjamin S.

    2014-01-01

    The principal mission of NASA Johnson Space Center is Human Spaceflight. In support of the mission the Applied Aeroscience and CFD Branch has several technical competencies that include aerodynamic characterization, aerothermodynamic heating, rarefied gas dynamics, and decelerator (parachute) systems.

  7. How to Apply for Protection Time Graphic

    EPA Pesticide Factsheets

    We will review insect repellent products that voluntarily apply to use the repellency awareness graphic to ensure that their scientific data meet current testing protocols and standard evaluation processes.

  8. Regulation of Skin-Applied Repellents

    EPA Pesticide Factsheets

    Before they can be marketed, most insect repellents must be registered by EPA, which indicates they have been evaluated and approved for human safety and effectiveness when applied according to label instructions.

  9. Applying the National Aquatic Resource Survey Data

    EPA Pesticide Factsheets

    The NARS generate nationally-consistent water quality data across a variety of indicators. States have applied the NARS data to help address local policy questions and to implement changes regarding aquatic resource management.

  10. Applied Physics at Heriot-Watt.

    ERIC Educational Resources Information Center

    Colles, M. J.

    1979-01-01

    Describes a course in applied physics with solid state electronics, aimed at providing a continuing broad background in general physics while allowing for the gradual development of an emphasis on applications, engineering expertise, and relevant industrial experience. (Author/GA)

  11. [Method and apparatus for applying metal cladding

    SciTech Connect

    Bosna, A.A.

    1989-09-27

    This progress report contains information related to the development of durable corrosion resistant coating materials for the hulls of ships and offshore platforms. Also contained are the details of an apparatus used to apply this material. (JEF)

  12. A Teaching Game for Applied Hydrobiology.

    ERIC Educational Resources Information Center

    Dussart, G. B. J.

    1981-01-01

    Provided are details for a game designed to help secondary school or college students understand the types of problems encountered in applied hydrobiology and the financial and time constraints involved in their solution. (PB)

  13. Applying or Implementing Nitrogen Dioxide Standards

    EPA Pesticide Factsheets

    Along with developing the NO2 standards themselves (part of the National Ambient Air Quality Standards, or NAAQS), EPA also develops requirements for how to apply or implement them, and work toward about attaining and maintaining those standards.

  14. Applied andrology in chickens and turkeys

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The theories and practices of applied andrology in commercial poultry species (turkey, layer chicken and broiler chicken) are reviewed. Poultry male reproductive biology, including reproductive anatomy and spermatogenesis, is compared with mammalian livestock species. A detailed description of pou...

  15. Applied-field MPD thruster geometry effects

    NASA Technical Reports Server (NTRS)

    Myers, Roger M.

    1991-01-01

    Eight MPD thruster configurations were used to study the effects of applied field strength, propellant, and facility pressure on thruster performance. Vacuum facility background pressures higher than approx. 0.12 Pa were found to greatly influence thruster performance and electrode power deposition. Thrust efficiency and specific impulse increased monotonically with increasing applied field strength. Both cathode and anode radii fundamentally influenced the efficiency specific impulse relationship, while their lengths influence only the magnitude of the applied magnetic field required to reach a given performance level. At a given specific impulse, large electrode radii result in lower efficiencies for the operating conditions studied. For all test conditions, anode power deposition was the largest efficiency loss, and represented between 50 and 80 pct. of the input power. The fraction of the input power deposited into the anode decreased with increasing applied field and anode radii. The highest performance measured, 20 pct. efficiency at 3700 seconds specific impulse, was obtained using hydrogen propellant.

  16. Security Science as an Applied Science?

    ERIC Educational Resources Information Center

    Smith, Clifton

    2001-01-01

    Describes the development of a security science degree as the emerging applied science of the protection of individuals and assets. Proposes the themes of physical, electronic, information security and facility management as scientific applications for the course. (Author/MM)

  17. Applying or Implementing Sulfur Dioxide Standards

    EPA Pesticide Factsheets

    Along with developing the SO2 standards themselves (part of the National Ambient Air Quality Standards, or NAAQS), EPA also develops requirements for how to apply or implement them, and work toward about attaining and maintaining those standards.

  18. Orienting and Applying Flux to Solar Cells

    NASA Technical Reports Server (NTRS)

    Feder, H.; Frasch, W.

    1982-01-01

    Solar cells are oriented and fluxed automatically at first work station along solar-array assembly line. In under 2 seconds rotary drive rotates cell into proper position for applying solder flux to bus pad on collector side. When contact bus pad is in correct position, capstan drive is disengaged, and vacuum holddown beneath cell is turned on. Flux system lowers and applies preset amount of solder flux to bus pad. Two interconnect tabs are soldered to fluxed areas.

  19. Applied Behavior Analysis in Flying Training Research.

    DTIC Science & Technology

    1980-01-01

    often referred to as behavior modification ) which promotes improvements in human learning through an analysis of the contingencies surrounding a...Company, in press. Bandura, A. Principles of behavior modification . New York: Holt, Rinehart & Winston, 1969. Bostow, D.E., & Bailey, J.S. Modification of...tutors for kindergarten children. Journal of Applied Behavior Analysis, 1974, 7, 223-232. Kazdin, A.E. Behavior modification in applied settings

  20. Applied Psychology in Europe: An ONR Perspective.

    DTIC Science & Technology

    1983-07-27

    RESOLUTION TEST CHART NATIONAL BUREAU OF STANDARDS- I963-A ONR LONOON REPORT R-7-83 ~, 0 04N9 OFFICEI F NAVAL ..of M IAPPLIED PSYCHOLOGY IN EUROPE...and Subtitle) S TYPE OF REPORT & PERIOD COVERED Applied Psychology in Europe: An ONR Assessment ’"PerspectivePrpci6v PERFORMING ORG. REPORT NUMBER 7...neceeeary end Identify by block nmber) Applied psychology Digital simulators Man-machine interfaces Performance models Combat reactions Memory enhancement 20

  1. Applied Physics. Course Materials: Physics 111, 112, 113. Seattle Tech Prep Applied Academics Project.

    ERIC Educational Resources Information Center

    South Seattle Community Coll., Washington.

    This publication contains materials for three courses in Applied Physics in the Applied Academics program at South Seattle Community College. It begins with the article, "Community College Applied Academics: The State of the Art?" (George B. Neff), which describes the characteristics, model, courses, and coordination activity that make…

  2. 34 CFR 400.4 - What definitions apply to the Vocational and Applied Technology Education Programs?

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Technology Education Programs? 400.4 Section 400.4 Education Regulations of the Offices of the Department of... APPLIED TECHNOLOGY EDUCATION PROGRAMS-GENERAL PROVISIONS § 400.4 What definitions apply to the Vocational and Applied Technology Education Programs? (a) Definitions in EDGAR. The following terms used...

  3. Applied Math. Course Materials: Math 111, 112, 113. Seattle Tech Prep Applied Academics Project.

    ERIC Educational Resources Information Center

    South Seattle Community Coll., Washington.

    This publication contains materials for three courses in Applied Math in the Applied Academics program at South Seattle Community College. It begins with the article, "Community College Applied Academics: The State of the Art?" (George B. Neff), which describes the characteristics, model, courses, and coordination activity that make up…

  4. Phenoxazine Based Units- Synthesis, Photophysics and Electrochemistry

    PubMed Central

    Nowakowska-Oleksy, Anna; Cabaj, Joanna

    2010-01-01

    A few new phenoxazine-based conjugated monomers were synthesized, characterized, and successfully used as semiconducting materials. The phenoxazine-based oligomers have low ionization potentials or high-lying HOMO levels (~4.7 eV), which were estimated from cyclic voltammetry. Conjugated oligomers offer good film—forming, mechanical and optical properties connected with their wide application. These results demonstrate that phenoxazine-based conjugated mers are a promising type of semiconducting and luminescent structures able to be used as thin films in organic electronics. PMID:20625802

  5. Applications of Scanning Tunneling Microscopy to Electrochemistry

    DTIC Science & Technology

    1990-05-29

    situ, and to investigate the well-defined Pt/I/Ag surface phases prepared by underpotential deposition (UPD) of Ag onto the iodine covered Pt surface... deposition and other electrochemical processes on dimensions that are not available with previous large (micron scale) electrodes. STM imaging

  6. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.; Oliver, D.J.

    1990-01-01

    The objective of this project is to provide the fundamental information on the mechanisms of bacterial leaching of pyrite. The knowledge of how bacterial leaching of pyrite functions is essential for design and development of a technology for coal cleaning with bacteria. The features of major electrochemical techniques will be examined to find out if any of them can provide a diagnostic information on the mechanisms of related reactions. The research was focused on how to improve the chemical activity of bacteria. Two major approaches were undertaken. One was to provide more nutrient salts. It was anticipated that by providing higher amounts of nutrients the concentration and the activity of bacteria would increase. The other approach was to provide fresh environment to bacteria for the growth. Before the experiments it was decided to first examine their activity with time. However, there was no literature information available on this subject. The effect of the solution pH, was also studied. 4 refs., 8 figs.

  7. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.

    1991-01-01

    The interactions of mineral-pyrite with T. ferrooxidans were studied by using a cyclic voltametry technique. The interactions with bacteria were examined during the entire growth stage of bacterial (fermentation). The pyrite surface invariably drastically changed its properties at the second day of fermentation. Beyond two days of fermentation, the cyclic voltamograms were insensitive to convective diffusion produced by stirring. The product layer was examined by SEM, X-ray diffraction and chemical analysis. The SEM study revealed that bacteria populated the pyrite surface at an extremely high density levels. The high density of bacteria, and the solid reaction products formed on the pyrite surface created conditions for pore diffusion which explained why the CVs became insensitive to convective diffusion in solution (stirring). The X-ray diffraction study confirmed jarosite as a product layer. A mechanism of T. ferrooxidans cells serving as nucleation sites for jarosite formation is proposed. 16 refs., 8 figs., 2 tabs.

  8. Electrochemistry of Thiobacillus ferroxidans reactions with pyrite

    SciTech Connect

    Pesic, B.; Oliver, D.J.

    1990-01-01

    The objective of this project is to provide the fundamental information on the mechanisms of bacterial leaching of pyrite. The knowledge of how bacterial leaching of pyrite functions is essential for design and development of a technology for coal cleaning with bacteria. The features of major electrochemical techniques will be examined to find out if any of them can provide a diagnostic information on the mechanisms of related reactions. This quarter the activity of T. ferrooxidans with duration of fermentation was examined. It was found that there were three distinct stages of fermentation. 1 fig.

  9. Applications of Scanning Tunneling Microscopy to Electrochemistry

    DTIC Science & Technology

    1988-10-28

    Stroscio, J.A.; Feenstra, ii.4.; Fain, A.P. Phys. Rev. Lett. 1987 U8, 1668-71. 17. Hamers, R.J.; Tromp, .M.; Demuth , J.E. Phys. &ev.Lett. 1986, 56, 1972-75...Feenstra, R.M.; Stroscio, J.A.; Fein, A.P. fLkL 1987, 181. 295-306. 49. Demuth , J.; Avouris, P. Phys. Today 1983, November, p 62. 50. Reihl, B.; Giazewski...F.C. In Electroanalytical Chemistry; Bard, A.J., Ed.; Marcel Dekker: Noy York, 1970; vol. 4, p 129. 64. Davis, J.M.; Fan, F-R.F.; Bard, A.J. J

  10. Single Entity Electrochemistry Progresses to Cell Counting.

    PubMed

    Gooding, J Justin

    2016-10-10

    Red blood cells have been counted in an electrochemical collision experiment recently described by Compton and co-workers. As a cell collides with the electrode it lyses and a current is observed from the reduction of oxygen from within the cell.

  11. DURIP Electrochemistry-Surface Spectroscopy Instrument

    DTIC Science & Technology

    1990-04-01

    proceed (at 0* C) for 2 hrs. After polymerization, the Anopore membrane was washed with degassed toluene, methanol (containing 5 % HCl), and pure... methanol . The membrane was then dried in vacuo. The resulting membranes were covered with thin films of polyacetylene. These thin surface layers were removed...membrane. Careful examination shows that the fibers are somewhat narrower than the 200 nrm diameter of the pores in the host membrane; the electron

  12. Impact Electrochemistry of Layered Transition Metal Dichalcogenides.

    PubMed

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

    2015-08-25

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

  13. In Vitro Electrochemistry of Biological Systems

    PubMed Central

    Adams, Kelly L.; Puchades, Maja; Ewing, Andrew G.

    2009-01-01

    This article reviews recent work involving electrochemical methods for in vitro analysis of biomolecules, with an emphasis on detection and manipulation at and of single cells and cultures of cells. The techniques discussed include constant potential amperometry, chronoamperometry, cellular electroporation, scanning electrochemical microscopy, and microfluidic platforms integrated with electrochemical detection. The principles of these methods are briefly described, followed in most cases with a short description of an analytical or biological application and its significance. The use of electrochemical methods to examine specific mechanistic issues in exocytosis is highlighted, as a great deal of recent work has been devoted to this application. PMID:20151038

  14. Hybrid electronics and electrochemistry with conjugated polymers.

    PubMed

    Inganäs, Olle

    2010-07-01

    In this critical review, we discuss the history and development of polymer devices wherein manipulation of the electronic conductivity by electrochemical redox processes in a conjugated polymer is used to form new functions. The devices employed are an electrochemical transistor, an electrolyte-gated field-effect transistor and light-emitting electrochemical cells, all of which combine doping/undoping of a conjugated polymer with modification of electronic transport (130 references).

  15. Electrochemistry of Water-Cooled Nuclear Reactors

    SciTech Connect

    Macdonald, Dgiby; Urquidi-Macdonald, Mirna; Pitt, Jonathan

    2006-08-08

    This project developed a comprehensive mathematical and simulation model for calculating thermal hydraulic, electrochemical, and corrosion parameters, viz. temperature, fluid flow velocity, pH, corrosion potential, hydrogen injection, oxygen contamination, stress corrosion cracking, crack growth rate, and other important quantities in the coolant circuits of water-cooled nuclear power plants, including both Boiling Water Reactors (BWRs) and Pressurized Water Reactors (PWRs). The model is being used to assess the three major operational problems in Pressurized Water Reactors (PWR), which include mass transport, activity transport, and the axial offset anomaly, and provide a powerful tool for predicting the accumulation of SCC damage in BWR primary coolant circuits as a function of operating history. Another achievement of the project is the development of a simulation tool to serve both as a training tool for plant operators and as an engineering test-bed to evaluate new equipment and operating strategies (normal operation, cold shut down and others). The development and implementation of the model allows us to estimate the activity transport or "radiation fields" around the primary loop and the vessel, as a function of the operating parameters and the water chemistry.

  16. Electrochemistry at Nanometer-Scaled Electrodes

    ERIC Educational Resources Information Center

    Watkins, John J.; Bo Zhang; White, Henry S.

    2005-01-01

    Electrochemical studies using nanometer-scaled electrodes are leading to better insights into electrochemical kinetics, interfacial structure, and chemical analysis. Various methods of preparing electrodes of nanometer dimensions are discussed and a few examples of their behavior and applications in relatively simple electrochemical experiments…

  17. 2015 CEC Annual Workshop on Electrochemistry

    DTIC Science & Technology

    2015-12-30

    for Diabetes Management. 11:30a-1:10p Lunch break. 1:10-2:00p Rebecca Lai, University of Nebraska-Lincoln Folding- and Dynamics-based...University of Texas at Austin “Glucose Monitoring for Diabetes Management” Adam Heller is Professor Emeritus in the McKetta Department of Chemical...Engineering at UT- Austin and consultant to Abbot Diabetes Care. Generally considered to represent the greatest triumph in the commercialization of

  18. Naval Surface Warfare Center Electrochemistry Branch

    DTIC Science & Technology

    1985-02-16

    MANUFACTURING 9 CORROSION PROTECTION _ v~~~~~~~~~~~~~~~~~~~~ LITHIUM BATTERY SAFEy 3 Batteries -Complex Electrochemical Systems A battery is a device for...submarines, etc.) in both the primary and the secondary versions. Reserve Lithium Thionyl Chloride Battery Prototype for Advanced Mine Versatile...be based primarily on the use of lithium as the anode material In elec- trochemical systems, this metal, which is the lightest metal known, exhibits

  19. Eigenstress model for electrochemistry of solid surfaces

    PubMed Central

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

    2016-01-01

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

  20. Electrochemistry of Some New Alkaline Battery Electrodes

    DTIC Science & Technology

    1976-02-01

    Roat ,1 ts of sume tests are s;hown in Ti qUrf :S o Io1 na ter~yn dry s torage, d.a s v Iabe to 01 a L i ri d~ ý,y)her 1)ro ce. se V 4 Not ) Di aRcba r...cal condi t.ons required fcs, such an apo: I cat i on- and Pro(.j6ýCt 01 OV’iera 1SyS tEI df.,sgr. Resulit,; of v~he eOtcve, prcqr’a:v led to the init

  1. Adaptive finite element methods in electrochemistry.

    PubMed

    Gavaghan, David J; Gillow, Kathryn; Süli, Endre

    2006-12-05

    In this article, we review some of our previous work that considers the general problem of numerical simulation of the currents at microelectrodes using an adaptive finite element approach. Microelectrodes typically consist of an electrode embedded (or recessed) in an insulating material. For all such electrodes, numerical simulation is made difficult by the presence of a boundary singularity at the electrode edge (where the electrode meets the insulator), manifested by the large increase in the current density at this point, often referred to as the edge effect. Our approach to overcoming this problem has involved the derivation of an a posteriori bound on the error in the numerical approximation for the current that can be used to drive an adaptive mesh-generation algorithm, allowing calculation of the quantity of interest (the current) to within a prescribed tolerance. We illustrate the generic applicability of the approach by considering a broad range of steady-state applications of the technique.

  2. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.; Oliver, D.J.; Kim, Inbeum; De, G.C.

    1993-01-20

    A cyclic voltammetry technique was used to study the interactions of pyrite during bioleaching with the bacterium Thiobacillus ferrooxidans. Potential effects of heavy metals (silver and mercury) and varying the pH on the iron oxidizing ability of the bacterium are reported. Redox potential techniques were used to study effect of ferrous sulfate concentration and pH on bacterial growth.

  3. Electrochemistry of Thiobacillus ferrooxidans reactions with pyrite

    SciTech Connect

    Pesic, B.

    1992-01-01

    The objective of this project is to provide the fundamental information on the mechanisms of bacterial leaching of pyrite. The knowledge of how bacterial leaching of pyrite functions is essential for design and development of a technology for coal cleaning with bacteria. The features of major electrochemical techniques will be examined to find out if any of them can provide a diagnostic information on the mechanisms of related reactions.

  4. Electrochemistry and spectroelectrochemistry of nitroxyl free radicals

    SciTech Connect

    Fish, J.R.; Swarts, S.G.; Sevilla, M.D.; Malinski, T.

    1988-06-30

    This work reports electrochemical and spectroelectrochemical studies of the two nitroxyl radicals 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (3-carbamoyl-PROXYL). Oxidation and reduction reactions have been observed in aqueous media over the pH range 2-12 in the potential range -0.8 to +0.8 V by differential pulse voltammetry, cyclic voltammetry, and thin-layer UV-visible spectroelectrochemistry, and the reaction products have been characterized by IR, NMR, and ESR spectrometry. At pH values less than 10, characteristic electrochemical behavior is observed to be analogous for both radicals, and the products from electron transfer compare quite favorably with those found by pulse radiolysis of aqueous solutions of nitroxyl radicals. At pH 2-9, a stable cation from a reversible oxidation and hydroxylamine following an irreversible reduction, as well as hydroxylated cation at pH higher than 9, are the same as those obtained in pulse radiolysis experiments. Spectroscopic evidence indicates that behavior following reduction at high pH differs for the two radicals. At pH 12, reduced TEMPO may undergo structural changes leading to the formation of a new radical consisting of a seven-membered ring.

  5. Applied kinesiology unreliable for assessing nutrient status.

    PubMed

    Kenney, J J; Clemens, R; Forsythe, K D

    1988-06-01

    Applied kinesiology is a technique used to assess nutritional status on the basis of the response of muscles to mechanical stress. In this study, 11 subjects were evaluated independently by three experienced applied kinesiologists for four nutrients (thiamin, zinc, vitamin A, and ascorbic acid). The results obtained by those applied kinesiologists were compared with (a) one another, (b) standard laboratory tests for nutrient status, and (c) computerized isometric muscle testing. Statistical analysis yielded no significant interjudge reliability, no significant correlation between the testers and standard biochemical tests for nutrient status, and no significant correlation between mechanical and manual determinations of relative muscle strength. In addition, the subjects were exposed in a double-blind fashion to supplements of thiamin, zinc, vitamin A, and ascorbic acid and two placebos (pectin and sucrose) and then re-tested. According to applied kinesiology theory, "weak" (indicating deficiency) muscles are strengthened when the subject is exposed to an appropriate nutritional supplement. Statistical analysis revealed no significant differences in the response to placebo, nutrients previously determined (by muscle testing) to be deficient, and nutrients previously determined (by muscle testing) to be adequate. Even though the number of subjects (11) and nutrients (4) tested was limited, the results of this study indicated that the use of applied kinesiology to evaluate nutrient status is no more useful than random guessing.

  6. [A critical review of applied criminology].

    PubMed

    Vollbach, Alexander

    2016-01-01

    By reporting on a recent decision of the Regional Court (LG) of Marburg (Germany) calling attention to applied criminology, a concept still insufficiently considered in the administration of criminal justice, the paper argues that professional action in the execution of the sentence represents nothing else but applied criminology. Based on this assumption, the paper discusses practical diagnosis and correctional planning. Beyond that, the paper deals with the future of criminology. In the opinion of the author an important aspect for the future of criminology will be if it will be able to remain in touch with the world in which we live, as an independent empirical science. Applied criminology and its methodology constitute the link between science and practice.

  7. Topically applied vitamins and their cutaneous effects.

    PubMed

    Grammaticopoulos, George T; Furtunopoulos, Demetrios G; Zisova, Lilia G

    2004-01-01

    The number of cosmetic products which include vitamins as a constituent has increased three-fold since 1991. Vitamins are commonly used as ingredients of products designed to improve the appearance and health of the skin; for this reason the cutaneous benefits of such products are actively researched by dermatologists and chemists. The present study does a review of the action of topically applied vitamins for local use which improves the function of the skin. We specifically consider the biologic activity of topically applied vitamins, their stability and usefulness. Ways of stabilizing different kinds of vitamins, as well as their stability to oxygen, light, temperature, acids, and bases, are shown. The conclusion suggested by the review is that the efficiency of topically applied vitamins is dependent not only on their good stabilization and concentration but also on the clinical individual tests that can determine the best product for each particular patient.

  8. Symbolic Interaction and Applied Social Research

    PubMed Central

    Kotarba, Joseph A.

    2014-01-01

    In symbolic interaction, a traditional yet unfortunate and unnecessary distinction has been made between basic and applied research. The argument has been made that basic research is intended to generate new knowledge, whereas applied research is intended to apply knowledge to the solution of practical (social and organizational) problems. I will argue that the distinction between basic and applied research in symbolic interaction is outdated and dysfunctional. The masters of symbolic interactionist thought have left us a proud legacy of shaping their scholarly thinking and inquiry in response to and in light of practical issues of the day (e.g., Znaniecki, and Blumer). Current interactionist work continues this tradition in topical areas such as social justice studies. Applied research, especially in term of evaluation and needs assessment studies, can be designed to serve both basic and applied goals. Symbolic interaction provides three great resources to do this. The first is its orientation to dynamic sensitizing concepts that direct research and ask questions instead of supplying a priori and often impractical answers. The second is its orientation to qualitative methods, and appreciation for the logic of grounded theory. The third is interactionism’s overall holistic approach to interfacing with the everyday life world. The primary illustrative case here is the qualitative component of the evaluation of an NIH-funded, translational medical research program. The qualitative component has provided interactionist-inspired insights into translational research, such as examining cultural change in medical research in terms of changes in the form and content of formal and informal discourse among scientists; delineating the impact of significant symbols such as "my lab" on the social organization of science; and appreciating the essence of the self-concept "scientist" on the increasingly bureaucratic and administrative identities of medical researchers. This

  9. Caldwell University's Department of Applied Behavior Analysis.

    PubMed

    Reeve, Kenneth F; Reeve, Sharon A

    2016-05-01

    Since 2004, faculty members at Caldwell University have developed three successful graduate programs in Applied Behavior Analysis (i.e., PhD, MA, non-degree programs), increased program faculty from two to six members, developed and operated an on-campus autism center, and begun a stand-alone Applied Behavior Analysis Department. This paper outlines a number of strategies used to advance these initiatives, including those associated with an extensive public relations campaign. We also outline challenges that have limited our programs' growth. These strategies, along with a consideration of potential challenges, might prove useful in guiding academicians who are interested in starting their own programs in behavior analysis.

  10. Velocity filtering applied to optical flow calculations

    NASA Technical Reports Server (NTRS)

    Barniv, Yair

    1990-01-01

    Optical flow is a method by which a stream of two-dimensional images obtained from a forward-looking passive sensor is used to map the three-dimensional volume in front of a moving vehicle. Passive ranging via optical flow is applied here to the helicopter obstacle-avoidance problem. Velocity filtering is used as a field-based method to determine range to all pixels in the initial image. The theoretical understanding and performance analysis of velocity filtering as applied to optical flow is expanded and experimental results are presented.

  11. Method of applying coatings to substrates

    DOEpatents

    Hendricks, Charles D.

    1991-01-01

    A method for applying novel coatings to substrates is provided. The ends of multiplicity of rods of different materials are melted by focused beams of laser light. Individual electric fields are applied to each of the molten rod ends, thereby ejecting charged particles that include droplets, atomic clusters, molecules, and atoms. The charged particles are separately transported, by the accelerations provided by electric potentials produced by an electrode structure, to substrates where they combine and form the coatings. Layered and thickness graded coatings comprised of hithereto unavailable compositions, are provided.

  12. System Applies Polymer Powder To Filament Tow

    NASA Technical Reports Server (NTRS)

    Baucom, Robert M.; Snoha, John J.; Marchello, Joseph M.

    1993-01-01

    Polymer powder applied uniformly and in continuous manner. Powder-coating system applies dry polymer powder to continuous fiber tow. Unique filament-spreading technique, combined with precise control of tension on fibers in system, ensures uniform application of polymer powder to web of spread filaments. Fiber tows impregnated with dry polymer powders ("towpregs") produced for preform-weaving and composite-material-molding applications. System and process valuable to prepreg industry, for production of flexible filament-windable tows and high-temperature polymer prepregs.

  13. Applying a Genetic Algorithm to Reconfigurable Hardware

    NASA Technical Reports Server (NTRS)

    Wells, B. Earl; Weir, John; Trevino, Luis; Patrick, Clint; Steincamp, Jim

    2004-01-01

    This paper investigates the feasibility of applying genetic algorithms to solve optimization problems that are implemented entirely in reconfgurable hardware. The paper highlights the pe$ormance/design space trade-offs that must be understood to effectively implement a standard genetic algorithm within a modem Field Programmable Gate Array, FPGA, reconfgurable hardware environment and presents a case-study where this stochastic search technique is applied to standard test-case problems taken from the technical literature. In this research, the targeted FPGA-based platform and high-level design environment was the Starbridge Hypercomputing platform, which incorporates multiple Xilinx Virtex II FPGAs, and the Viva TM graphical hardware description language.

  14. Defining applied behavior analysis: An historical analogy

    PubMed Central

    Deitz, Samuel M.

    1982-01-01

    This article examines two criteria for a definition of applied behavior analysis. The criteria are derived from a 19th century attempt to establish medicine as a scientific field. The first criterion, experimental determinism, specifies the methodological boundaries of an experimental science. The second criterion, philosophic doubt, clarifies the tentative nature of facts and theories derived from those facts. Practices which will advance the science of behavior are commented upon within each criteria. To conclude, the problems of a 19th century form of empiricism in medicine are related to current practices in applied behavior analysis. PMID:22478557

  15. The Master's Thesis in Applied Psychology Training.

    ERIC Educational Resources Information Center

    Shultz, Kenneth S.; Kottke, Janet L.

    1996-01-01

    Recommends the inclusion of a master's thesis in industrial and organizational psychology programs. Argues that the thesis serves several critical educational purposes and is relevant to applied psychology. Offers suggestions for increasing the relationship between the educational requirement and the professional tasks. (MJP)

  16. Learning for Life: Applying the AASL Standards

    ERIC Educational Resources Information Center

    Franklin, Pat; Stephens, Claire Gatrell

    2010-01-01

    When the American Association of School Librarians (AASL) first released the new Standards for the 21st-Century Learner, controversy arose because many school librarians thought that they were vague and de-emphasized information skill instruction. Many school librarians had trouble visualizing how the program would be applied in their school and…

  17. Applied programs at Brookhaven National Laboratory

    SciTech Connect

    Not Available

    1991-09-01

    This document overviews the areas of current research at Brookhaven National Laboratory. Technology transfer and the user facilities are discussed. Current topics are presented in the areas of applied physics, chemical science, material science, energy efficiency and conservation, environmental health and mathematics, biosystems and process science, oceanography, and nuclear energy. (GHH)

  18. Applying Automated Theorem Proving to Computer Security

    DTIC Science & Technology

    2008-03-01

    Based Access Control. International Journal of Applied Mathematics and Computer Science, 12(2), 2002. LM82. A. Lockman and N. Minsky . Unidirectional...Min78. N. Minsky . An Operation-Control Scheme for Authorization in Com- puter Systems. International Journal of Computing and Information Sciences, June

  19. Applied fluvial geomorphology. Report No. 31

    SciTech Connect

    MacBroom, J.G.

    1981-03-01

    The first portion of this report discusse the geologic properties and characteristics of natural rivers and floodplains. The second part outlines the influence of man on fluvial geomorphology, ecological considerations, and the natural characteristics of rivers that should be applied in the design of river and bridge projects.

  20. Applied fluvial geomorphology. Report No. 31

    SciTech Connect

    MacBroom, J.G.

    1981-03-01

    The first portion of this report discusses the geologic properties and characteristics of natural rivers and floodplains. The second part outlines the influence of man on fluvial geomorphology, ecological considerations, and the natural characteristics of rivers that should be applied in the design of river and bridge projects.

  1. Educating and Training Undergraduate Applied Statisticians.

    ERIC Educational Resources Information Center

    Peres, Clovis A.; And Others

    1985-01-01

    A course on Applied Statistics, offered since 1978 at the Instituto de Matematica e Estatistica, Universidade de Sao Paulo, Brasil, is designed to educate statisticians at the bachelor's level for jobs in government statistical offices, industry, and business. (Author/LMO)

  2. Second Language Acquisition: Research and Applied Linguistics.

    ERIC Educational Resources Information Center

    Pica, Teresa

    2003-01-01

    This paper provides an overview of second language acquisition (SLA) research over the past several decades and highlights the ways in which it has retained its original applied and linguistic interests and enhanced them by addressing questions about acquisition processes. After discussing disciplinary contexts (SLA research and applied…

  3. Applied Biomechanics in an Instructional Setting

    ERIC Educational Resources Information Center

    Hudson, Jackie L.

    2006-01-01

    Biomechanics is the science of how people move better, meaning more skillfully and more safely. This article places more emphasis on skill rather than safety, though there are many parallels between them. It shares a few features of the author's paradigm of applied biomechanics and discusses an integrated approach toward a middle school football…

  4. Applying Cryopreservation Techniques to Diverse Biological Materials

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Developing new cryopreservation protocols for each new plant or tissue is time consuming and often unnecessary. Existing standard protocols can be applied to many plants resulting in moderate to excellent results or protocols may require only a few changes for optimum recovery of plants. Protocols ...

  5. Newspaper Twitter: Applied Drama and Microblogging

    ERIC Educational Resources Information Center

    Wotzko, Rebecca

    2012-01-01

    This paper discusses the use of applied drama within the microblogging platform "Twitter" as a method to increase students' social media and news literacy. Online news sites are increasingly using "Twitter" as a source for eyewitness accounts of events or public opinion. "Twitter" offers users a simple way to publicly…

  6. Plenary Speeches: Applied Linguists without Borders

    ERIC Educational Resources Information Center

    Tarone, Elaine

    2013-01-01

    Until 1989, the American Association for Applied Linguistics (AAAL) could have been viewed as an interest group of the Linguistics Society of America (LSA); AAAL met in two designated meeting rooms as a subsection of the LSA conference. In 1991, I was asked to organize the first independent meeting of AAAL in New York City, with the help of…

  7. Ideology in Applied Linguistics for Language Teaching

    ERIC Educational Resources Information Center

    Waters, Alan

    2009-01-01

    It is contended that much of present-day applied linguistics for language teaching (ALLT) fails to mediate effectively, primarily because an ideological construction, emanating from a critical theory perspective, is too often imposed on everyday pedagogical practices. This has resulted in an exaggerated level of concern about the power imbalances…

  8. Applying Brain-Friendly Instructional Practices

    ERIC Educational Resources Information Center

    Erlauer-Myrah, Laura

    2006-01-01

    In this article, the author offers advice for principals on working with teachers to change the instructional climate and on how to apply brain-friendly instructions to improve the effectiveness of one's teaching. To lead an entire district toward the use of brain-compatible instruction, the author suggests to start with a group of motivated…

  9. Second Language Acquisition and Applied Linguistics.

    ERIC Educational Resources Information Center

    Larsen-Freeman, Diane

    2000-01-01

    Discusses the second language acquisition (SLA) process and the differential success of second language learners. Examines the fundamental challenges that this characterization faces, and highlights the contributions SLA is capable of in the coming decade. Offers topics for a training and development of curriculum for future applied linguists from…

  10. An Innovative Baccalaureate Degree: Applied versus Traditional

    ERIC Educational Resources Information Center

    Arney, Janna B.; Hardebeck, Suzanne; Estrada, Joselito; Permenter, Vivian

    2006-01-01

    The bachelor of applied arts and sciences (BAAS) degree is a baccalaureate program designed to meet the needs of nontraditional students by allowing technical hours to be transferred for credit to a baccalaureate degree. To determine if the university was positively serving the needs of its constituents, salaries of BAAS graduates were compared to…

  11. Applied Behavior Analysis: Beyond Discrete Trial Teaching

    ERIC Educational Resources Information Center

    Steege, Mark W.; Mace, F. Charles; Perry, Lora; Longenecker, Harold

    2007-01-01

    We discuss the problem of autism-specific special education programs representing themselves as Applied Behavior Analysis (ABA) programs when the only ABA intervention employed is Discrete Trial Teaching (DTT), and often for limited portions of the school day. Although DTT has many advantages to recommend its use, it is not well suited to teach…

  12. Positive Behavior Support and Applied Behavior Analysis

    ERIC Educational Resources Information Center

    Johnston, J. M.; Foxx, R. M.; Jacobson, J. W.; Green, G.; Mulick, J. A.

    2006-01-01

    This article reviews the origins and characteristics of the positive behavior support (PBS) movement and examines those features in the context of the field of applied behavior analysis (ABA). We raise a number of concerns about PBS as an approach to delivery of behavioral services and its impact on how ABA is viewed by those in human services. We…

  13. Applied Behavior Analysis as Technological Science.

    ERIC Educational Resources Information Center

    Iwata, Brian A.

    1991-01-01

    To the extent that applied behavior analysis represents a scientific and practical approach to the study of behavior, its technological character is essential. The most serious problem evident in the field is not that the research being done is too technical but that more good research of all types is needed. (JDD)

  14. Uniform insulation applied-B ion diode

    DOEpatents

    Seidel, David B.; Slutz, Stephen A.

    1988-01-01

    An applied-B field extraction ion diode has uniform insulation over an anode surface for increased efficiency. When the uniform insulation is accomplished with anode coils, and a charge-exchange foil is properly placed, the ions may be focused at a point on the z axis.

  15. Applied Art in Trade and Industrial Education.

    ERIC Educational Resources Information Center

    King, Annie; Zirkle, Chris

    Ohio Hi-Point Joint Vocational School (JVS) has developed a comprehensive art program within the vocational setting. Selected trade and industrial programs at the school, as well as programs in agriculture and home economics, incorporate art instruction. The goals of the applied art program are as follows: to give students the opportunity to…

  16. Engineering and Applied Science, Recent Research Reports.

    ERIC Educational Resources Information Center

    National Science Foundation, Washington, DC. Directorate of Engineering and Applied Science.

    This collection contains abstracts of technical reports and journal articles resulting from research funded by the National Science Foundation. Included in the collection are abstracts arranged in several categories: (1) electrical, computer, and systems engineering; (2) civil and mechanical engineering; (3) applied research; (4) problem-focused…

  17. Applied groundwater modeling, 2nd Edition

    USGS Publications Warehouse

    Anderson, Mary P.; Woessner, William W.; Hunt, Randall J.

    2015-01-01

    This second edition is extensively revised throughout with expanded discussion of modeling fundamentals and coverage of advances in model calibration and uncertainty analysis that are revolutionizing the science of groundwater modeling. The text is intended for undergraduate and graduate level courses in applied groundwater modeling and as a comprehensive reference for environmental consultants and scientists/engineers in industry and governmental agencies.

  18. Thermodynamic Laws Applied to Economic Systems

    ERIC Educational Resources Information Center

    González, José Villacís

    2009-01-01

    Economic activity in its different manifestations--production, exchange, consumption and, particularly, information on quantities and prices--generates and transfers energy. As a result, we can apply to it the basic laws of thermodynamics. These laws are applicable within a system, i.e., in a country or between systems and countries. To these…

  19. Applying College Credit to a Noncollegiate Program

    ERIC Educational Resources Information Center

    McGarraghy, John J.

    1976-01-01

    Describes the evaluation process as it was applied at the Life Office Management Association (LOMA)-the first organization to have a nationally conducted adult education program evaluated. Information about other noncollegiate sponsored programs for college credit is also provided. (ABM)

  20. Applied Creativity: The Creative Marketing Breakthrough Model

    ERIC Educational Resources Information Center

    Titus, Philip A.

    2007-01-01

    Despite the increasing importance of personal creativity in today's business environment, few conceptual creativity frameworks have been presented in the marketing education literature. The purpose of this article is to advance the integration of creativity instruction into marketing classrooms by presenting an applied creative marketing…

  1. Research Design and Statistics for Applied Linguistics.

    ERIC Educational Resources Information Center

    Hatch, Evelyn; Farhady, Hossein

    An introduction to the conventions of research design and statistical analysis is presented for graduate students of applied linguistics. The chapters cover such concepts as the definition of research, variables, research designs, research report formats, sorting and displaying data, probability and hypothesis testing, comparing means,…

  2. Political Economy in Applied Linguistics Research

    ERIC Educational Resources Information Center

    Block, David

    2017-01-01

    This state-of-the-art review is based on the fundamental idea that political economy should be adopted as a frame for research and discussion in applied linguistics as part of a general social turn which has taken hold in the field over the past three decades. It starts with Susan Gal's (1989) early call for such a move in sociolinguistics and…

  3. Applying Servant Leadership in Today's Schools

    ERIC Educational Resources Information Center

    Culver, Mary K.

    2009-01-01

    This book illustrates how the ideal of servant leadership can be applied in your school today. With real-life scenarios, discussions, and self assessments, this book gives practical suggestions to help you develop into a caring and effective servant leader. There are 52 scenarios in this book, focusing on situations as varied as: (1) Dealing with…

  4. Applied Mathematics in the Undergraduate Curriculum.

    ERIC Educational Resources Information Center

    Committee on the Undergraduate Program in Mathematics, Berkeley, CA.

    After considering the growth in the use of mathematics in the past 25 years, this report makes four major recommendations regarding the undergraduate curriculum: (1) The mathematics department should offer a course or two in applied mathematics which treat some realistic situations completely, including the steps of problem formulation, model…

  5. Applying Mechanics to Swimming Performance Analysis.

    ERIC Educational Resources Information Center

    Barthels, Katharine

    1989-01-01

    Swimming teachers and coaches can improve their feedback to swimmers, when correcting or refining swim movements, by applying some basic biomechanical concepts relevant to swimming. This article focuses on the biomechanical considerations used in analyzing swimming performance. Techniques for spotting and correcting problems that impede…

  6. Applying Social Psychological Concepts Outside the Classroom

    ERIC Educational Resources Information Center

    Lakin, Jessica L.; Wichman, Aaron L.

    2005-01-01

    This article evaluates a writing assignment in which social psychology students gathered examples from outside the classroom (e.g., cartoons, movies) and analyzed them with course material. Compared to a control group, students who completed the assignment learned that it was easier to apply social psychology to the real world. A follow-up survey…

  7. Visualisation in Applied Learning Contexts: A Review

    ERIC Educational Resources Information Center

    Twissell, Adrian

    2014-01-01

    This literature review explores visualisation within the context of learning in design, engineering and technology education. The investigation first defines visualisation, providing examples of activities that utilise visualisation skills within an applied field. Then exploration of the mental mechanisms of visualisation used to engage with those…

  8. Applying Technology in the Work Environment.

    ERIC Educational Resources Information Center

    Greenwood, Reed, Ed.

    A series of papers is presented from two symposia sponsored by the Work Environment and Technology Committee and offered at annual conferences of the President's Committee on Employment of People with Disabilities. The 1988 symposium was called "Applying Technology in the Work Environment" and the 1989 symposium was called "Reasonable…

  9. Introduction: Conversation Analysis in Applied Linguistics

    ERIC Educational Resources Information Center

    Sert, Olcay; Seedhouse, Paul

    2011-01-01

    This short, introductory paper presents an up-to-date account of works within the field of Applied Linguistics which have been influenced by a Conversation Analytic paradigm. The article reviews recent studies in classroom interaction, materials development, proficiency assessment and language teacher education. We believe that the publication of…

  10. Applied Welding Technology. Technical Committee Report.

    ERIC Educational Resources Information Center

    Idaho State Dept. of Education, Boise. Div. of Vocational Education.

    This Technical Committee Report prepared by industry representatives in Idaho lists the skills currently necessary for an employee in that state to obtain a job in applied welding technology, retain a job once hired, and advance in that occupational field. (Task lists are grouped according to duty areas generally used in industry settings, and are…

  11. Edinburgh Working Papers in Applied Linguistics, 1997.

    ERIC Educational Resources Information Center

    Mitchell, Keith, Ed.; Parkinson, Brian, Ed.

    1997-01-01

    Papers on applied linguistics and language pedagogy include: "A Genre Analysis Study of 80 Medical Abstracts" (Kenneth Anderson, Joan Maclean); "Oral Classroom Testing in an Adult French Community Class" (Sheena Davies, Aileen Irvine, Jacqueline Larrieu); "Whose Relevance? Interpretation of Hybrid Texts by a Multiple…

  12. A Primer on Disseminating Applied Quantitative Research

    ERIC Educational Resources Information Center

    Bell, Bethany A.; DiStefano, Christine; Morgan, Grant B.

    2010-01-01

    Transparency and replication are essential features of scientific inquiry, yet scientific communications of applied quantitative research are often lacking in much-needed procedural information. In an effort to promote researchers dissemination of their quantitative studies in a cohesive, detailed, and informative manner, the authors delineate…

  13. Center for Applied Linguistics, Washington DC, USA

    ERIC Educational Resources Information Center

    Sugarman, Julie; Fee, Molly; Donovan, Anne

    2015-01-01

    The Center for Applied Linguistics (CAL) is a private, nonprofit organization with over 50 years' experience in the application of research on language and culture to educational and societal concerns. CAL carries out its mission to improve communication through better understanding of language and culture by engaging in a variety of projects in…

  14. How To Apply For a Broadcast Station.

    ERIC Educational Resources Information Center

    Federal Communications Commission, Washington, DC.

    Procedures for receiving permission from the Federal Communications Commission (FCC) for authority to construct a radio or television broadcast station are outlined. Instructions for selecting a facility, applying for a construction permit, and giving local notice of intentions are included, along with sections on the hearing procedure,…

  15. Applied Literature and Composition Curriculum Guide.

    ERIC Educational Resources Information Center

    Georgia State Dept. of Education, Atlanta.

    Redesigned to reflect a more standards-driven as opposed to course-driven approach, the Applied Literature and Composition courses (I and II) described in this paper not only prepare the two-year college/technical school students for entering the real world of work, but also for post-secondary and college level work. It notes that the course is…

  16. Applied Linguistics and Primary School Teaching

    ERIC Educational Resources Information Center

    Ellis, Sue, Ed.; McCartney, Elspeth, Ed.

    2011-01-01

    Modern primary teachers must adapt literacy programmes and ensure efficient learning for all. They must also support children with language and literacy difficulties, children learning English as an additional language and possibly teach a modern foreign language. To do this effectively, they need to understand the applied linguistics research…

  17. The Moral Self: Applying Identity Theory

    ERIC Educational Resources Information Center

    Stets, Jan E.; Carter, Michael J.

    2011-01-01

    This research applies identity theory to understand the moral self. In identity theory, individuals act on the basis of their identity meanings, and they regulate the meanings of their behavior so that those meanings are consistent with their identity meanings. An inconsistency produces negative emotions and motivates individuals to behave…

  18. Problems Portraying Migrants in Applied Linguistics Research

    ERIC Educational Resources Information Center

    Block, David

    2010-01-01

    This paper is a very personal attempt to explore the problematics of portraying migrants in Applied Linguistics research. I begin with a discussion of identity, in particular what we might mean when we use the term, and from there I go on to explore its fundamental imprecision through an analysis of a census question about ethnicity. I then…

  19. Populations, Natural Selection, and Applied Organizational Science.

    ERIC Educational Resources Information Center

    McKelvey, Bill; Aldrich, Howard

    1983-01-01

    Deficiencies in existing models in organizational science may be remedied by applying the population approach, with its concepts of taxonomy, classification, evolution, and population ecology; and natural selection theory, with its principles of variation, natural selection, heredity, and struggle for existence, to the idea of organizational forms…

  20. Psycholinguistics in Applied Linguistics: Trends and Perspectives.

    ERIC Educational Resources Information Center

    de Bot, Kees

    2000-01-01

    Discusses the relationship between the terms psycholinguistics and applied linguistics, and in the process explores key issues in multilingual processing, such as the structure of the bilingual lexicon, language choice in production and perception, and the language mode. (Author/VWL)