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.

2015 CEC Annual Workshop on Electrochemistry

DTIC Science & Technology

2015-12-30

Street Suite 5.300 Austin , TX 78712 -1532 23-Aug-2015 ABSTRACT Number of Papers published in peer-reviewed journals: Number of Papers published in non peer...SECURITY CLASSIFICATION OF: The Center for Electrochemistry (CEC) at the University of Texas at Austin held its seventh annual electrochemistry...workshop February 7–8, 2015 in Welch Hall on the campus of The University of Texas at Austin . There were 160 registered attendees for this conference

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

PubMed

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

2014-02-01

The direct electrochemistry of glucose oxidase (GOx) was successfully realized on electrochemically reduced graphene oxide and silver nanoparticles (RGO/Ag) nanocomposite modified electrode. The fabricated nanocomposite was characterized by field emission scanning electron microscope and energy dispersive spectroscopy. The GOx immobilized nanocomposite modified electrode showed a pair of well-defined redox peaks with a formal potential (E°) of -0.422 V, indicating that the bioactivity of GOx was retained. The heterogeneous electron transfer rate constant (Ks) of GOx at the nanocomposite was calculated to be 5.27 s(-1), revealing a fast direct electron transfer of GOx. The GOx immobilized RGO/Ag nanocomposite electrode exhibited a good electrocatalytic activity toward glucose over a linear concentration range from 0.5 to 12.5 mM with a detection limit of 0.16 mM. Besides, the fabricated biosensor showed an acceptable sensitivity and selectivity for glucose. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrochemistry at One Nanoparticle.

PubMed

Mirkin, Michael V; Sun, Tong; Yu, Yun; Zhou, Min

2016-10-18

Electrochemistry at metal nanoparticles (NPs) is of significant current interest because of its applications in catalysis, energy conversion and storage, and sensors. The electrocatalytic activity of NPs depends strongly on their size, shape, and surface attachment. The use of a large number of particles in most reported kinetic experiments obscured the effects of these factors because of polydispersity and different NP orientations. Recent efforts to probe electrochemistry at single NPs included recording of the catalytically amplified current produced by random collisions of particles with the electrode surface, immobilizing an NP on the surface of a small electrode, and delivering individual NPs to electrode surfaces. Although the signals recorded in such experiments were produced by single NPs, the characterization issues and problems with separating an individual particle from other NPs present in the system made it difficult to obtain spatially and/or temporally resolved information about heterogeneous processes occurring at a specific NP. To carry out electrochemical experiments involving only one NP and characterize such an NP in situ, one needs nanoelectrochemical tools with the characteristic dimension smaller than or comparable to those of the particle of interest. This Account presents fundamentals of two complementary approaches to studying NP electrochemistry, i.e., probing single immobilized NPs with the tip of a scanning electrochemical microscope (SECM) and monitoring the collisions between one catalytic NP and a carbon nanopipette. The former technique can provide spatially resolved information about NP geometry and measure its electron transfer properties and catalytic activity under steady-state conditions. The emphasis here is on the extraction of quantitative physicochemical information from nanoelectrochemical data. By employing a polished disk-type nanoelectrode as an SECM tip, one can characterize a specific nanoparticle in situ and then

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

PubMed

Shervedani, Reza Karimi; Amini, Akbar

2012-04-01

Direct electrochemistry of a new laccase enzyme immobilized on gold and its application as a biosensor for dopamine (DA) are investigated by voltammetry and electrochemical impedance spectroscopy. The sensor demonstrated a redox adsorption behavior with E(0') = + 180 mV vs. Ag/AgCl for immobilized Agaricus bisporus laccase (LacAB) enzyme. The MPA platform was assembled on Au with and without utilization of ultrasounds. Excellent results were obtained by using the enzyme electrode fabricated based on MPA assembled with sonication. The LacAB immobilized in this condition showed a large electrocatalytic activity for oxidation of DA. Accordingly, a third-generation (mediator free) biosensor was constructed for DA. The DA concentration could be measured in the linear range of 0.5 to 13.0 and 47.0 to 430.0 μmol L(-1) with correlation coefficients of 0.999 and 0.989, respectively, and a detection limit of 29.0 nmol L(-1). The biosensor was successfully tested for determination of DA in human blood plasma and pharmaceutical samples. Copyright © 2011 Elsevier B.V. All rights reserved.

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

PubMed

Shi, Fan; Xi, Jingwen; Hou, Fei; Han, Lin; Li, Guangjiu; Gong, Shixing; Chen, Chanxing; Sun, Wei

2016-01-01

In this paper a three-dimensional (3D) reduced graphene oxide (RGO) and gold (Au) composite was synthesized by electrodeposition and used for the electrode modification with carbon ionic liquid electrode (CILE) as the substrate electrode. Myoglobin (Mb) was further immobilized on the surface of 3D RGO-Au/CILE to obtain an electrochemical sensing platform. Direct electrochemistry of Mb on the modified electrode was investigated with a pair of well-defined redox waves appeared on cyclic voltammogram, indicating the realization of direct electron transfer of Mb with the modified electrode. The results can be ascribed to the presence of highly conductive 3D RGO-Au composite on the electrode surface that accelerate the electron transfer rate between the electroactive center of Mb and the electrode. The Mb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid in the concentration range from 0.2 to 36.0 mmol/L with the detection limit of 0.06 mmol/L (3σ). Copyright © 2015 Elsevier B.V. All rights reserved.

Direct Electrochemistry of Bilirubin Oxidase from Magnaporthe orizae on Covalently-Functionalized MWCNT for the Design of High-Performance Oxygen-Reducing Biocathodes.

PubMed

Gentil, Solène; Carrière, Marie; Cosnier, Serge; Gounel, Sébastien; Mano, Nicolas; Le Goff, Alan

2018-06-12

Herein, the direct electrochemistry of bilirubin oxidase from Magnaporthe orizae (MoBOD) was studied on CNTs functionalized by electrografting several types of diazonium salts. The functionalization induces favorable or unfavorable orientation of MoBOD, the latter being compared to the well-known BOD from Myrothecium verrucaria (MvBOD). On the same nanostructured electrodes, MoBOD can surpass MvBOD in terms of both current densities and minimal overpotentials. Added to the fact that MoBOD is also highly active at the gas-diffusion electrode (GDE), these findings make MoBOD one of the MCOs with the highest catalytic activity towards the oxygen reduction reaction (ORR). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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…

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

PubMed

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

2013-01-08

In this work, a new label-free electrochemical aptamer-based sensor (aptasensor) was constructed for detection of platelet-derived growth factor (PDGF) based on the direct electrochemistry of glucose oxidase (GOD). For this proposed aptasensor, poly(diallyldimethylammonium chloride) (PDDA)-protected graphene-gold nanoparticles (P-Gra-GNPs) composite was firstly coated on electrode surface to form the interface with biocompatibility and huge surface area for the adsorption of GOD layer. Subsequently, gold nanoclusters (GNCs) were deposited on the surface of GOD to capture PDGF binding aptamer (PBA). Finally, GOD as a blocking reagent was employed to block the remaining active sites of the GNCs and avoid the nonspecific adsorption. With the direct electron transfer of double layer GOD membranes, the aptasensor showed excellent electrochemical response and the peak current decreased linearly with increasing logarithm of PDGF concentration from 0.005 nM to 60 nM with a relatively low limit of detection of 1.7 pM. The proposed aptasensor exhibited high specificity, good reproducibility and long-term stability, which provided a new promising technique for aptamer-based protein detection. Copyright © 2012 Elsevier B.V. All rights reserved.

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

An Effective Approach to Teaching Electrochemistry.

ERIC Educational Resources Information Center

Birss, Viola I.; Truax, D. Rodney

1990-01-01

An approach which may be useful for teaching electrochemistry in freshman college chemistry courses is presented. Discussed are the potential problems with teaching this subject and solutions provided by this approach. (CW)

The birth of protein electrochemistry.

PubMed

Blanford, Christopher F

2013-12-11

The results from a final-year undergraduate project led to an $876M sale of a spin-out company 19 years later: the 1977 communication from Mark Eddowes and Allen Hill seeded the rich field of protein electrochemistry, the technology that underpins commercial glucose biosensors.

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

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

PubMed

Evans, Rhiannon M; Armstrong, Fraser A

2014-01-01

Protein film electrochemistry is a technique which allows the direct control of redox-active enzymes, providing particularly detailed information on their catalytic properties. The enzyme is deposited onto a working electrode tip, and through control of the applied potential the enzyme activity is monitored as electrical current, allowing for direct study of inherent activity as electrons are transferred to and from the enzyme redox center(s). No mediators are used. Because the only enzyme present in the experiment is bound at the electrode surface, gaseous and liquid phase inhibitors can be introduced and removed whilst the enzyme remains in situ. Potential control means that kinetics and thermodynamics are explored simultaneously; the kinetics of a reaction can be studied as a function of potential. Steady-state catalytic rates are observed directly as current (for a given potential) and non-steady-state rates (such as interconversions between different forms of the enzyme) are observed from the change in current with time. The more active the enzyme, the higher the current and the better the signal-to-noise. In this chapter we outline the practical aspects of PFE for studying electroactive enzymes, using the Escherichia coli [NiFe]-hydrogenase 1 (Hyd-1) as an example.

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

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

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

PubMed

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

2014-10-15

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

Electrochemistry and Storage

NASA Technical Reports Server (NTRS)

Thaller, L. H.

1984-01-01

The term electrochemistry implies the use of devices that convert chemical energy into electrical energy and sometimes vice versa. These devices are usually composed of some number of individual cells that are connected together to form a battery. In the cases where these devices cannot be electrically recharged they are usually referred to as primary batteries, whereas if these batteries can be charged and recharged repeatedly, they are called secondary batteries. The past and present uses of primary and secondary batteries in aerospace applications are discussed.

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

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.

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.

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

PubMed

Cheng, Fangyi; Chen, Jun

2012-03-21

Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references).

Individuals Achieve More Accurate Results with Meters That Are Codeless and Employ Dynamic Electrochemistry

PubMed Central

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

2010-01-01

Background Studies have shown that controlling blood glucose can reduce the onset and progression of the long-term microvascular and neuropathic complications associated with the chronic course of diabetes mellitus. Improved glycemic control can be achieved by frequent testing combined with changes in medication, exercise, and diet. Technological advancements have enabled improvements in analytical accuracy of meters, and this paper explores two such parameters to which that accuracy can be attributed. Methods Four blood glucose monitoring systems (with or without dynamic electrochemistry algorithms, codeless or requiring coding prior to testing) were evaluated and compared with respect to their accuracy. Results Altogether, 108 blood glucose values were obtained for each system from 54 study participants and compared with the reference values. The analysis depicted in the International Organization for Standardization table format indicates that the devices with dynamic electrochemistry and the codeless feature had the highest proportion of acceptable results overall (System A, 101/103). Results were significant when compared at the 10% bias level with meters that were codeless and utilized static electrochemistry (p = .017) or systems that had static electrochemistry but needed coding (p = .008). Conclusions Analytical performance of these blood glucose meters differed significantly depending on their technologic features. Meters that utilized dynamic electrochemistry and did not require coding were more accurate than meters that used static electrochemistry or required coding. PMID:20167178

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

PubMed

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

2010-01-01

Studies have shown that controlling blood glucose can reduce the onset and progression of the long-term microvascular and neuropathic complications associated with the chronic course of diabetes mellitus. Improved glycemic control can be achieved by frequent testing combined with changes in medication, exercise, and diet. Technological advancements have enabled improvements in analytical accuracy of meters, and this paper explores two such parameters to which that accuracy can be attributed. Four blood glucose monitoring systems (with or without dynamic electrochemistry algorithms, codeless or requiring coding prior to testing) were evaluated and compared with respect to their accuracy. Altogether, 108 blood glucose values were obtained for each system from 54 study participants and compared with the reference values. The analysis depicted in the International Organization for Standardization table format indicates that the devices with dynamic electrochemistry and the codeless feature had the highest proportion of acceptable results overall (System A, 101/103). Results were significant when compared at the 10% bias level with meters that were codeless and utilized static electrochemistry (p = .017) or systems that had static electrochemistry but needed coding (p = .008). Analytical performance of these blood glucose meters differed significantly depending on their technologic features. Meters that utilized dynamic electrochemistry and did not require coding were more accurate than meters that used static electrochemistry or required coding. 2010 Diabetes Technology Society.

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

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

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. © 2011 Bentham Science Publishers Ltd.

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.

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.…

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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthetic Organic Electrochemistry: Calling All Engineers.

PubMed

Yan, Ming; Kawamata, Yu; Baran, Phil S

2018-04-09

Unmet potential: Electrochemistry is the most simple and basic way of altering the redox-states of organic molecules. Despite extensive studies and its demonstrated promise, it has yet to take off in mainstream synthesis. The reason is due to engineering challenges in instrument design. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

ERIC Educational Resources Information Center

Hendel, Samuel J.; Young, Elizabeth R.

2016-01-01

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

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)

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.

Ultrasensitive thrombin detection based on direct electrochemistry of highly loaded hemoglobin spheres-encapsulated platinum nanoparticles as labels and electrocatalysts.

PubMed

Wu, Yongmei; Xu, Wenju; Bai, Lijuan; Yuan, Yali; Yi, Huayu; Chai, Yaqin; Yuan, Ruo

2013-12-15

For the first time, a sandwich-type electrochemical method was proposed for ultrasensitive thrombin (TB) detection based on direct electrochemistry of highly loaded hemoglobin spheres-encapsulated platinum nanoparticles (PtNPs@Hb) as labels and electrocatalysts. The prepared PtNPs@Hb not only exhibited good biocompatibility, excellent electrocatalytic activity, but also presented redox activity of Hb. Thus, it was employed for the fabrication of aptasensor without any extraneous redox mediators, leading to a simple preparation process for the aptasensor. The high loading of Hb spheres as redox mediators could enhance the electrochemical signal. Importantly, the synergetic electrocatalytic behavior of Hb and PtNPs toward H2O2 reduction greatly amplified the electrochemical signal, resulting in the high sensitivity of aptasensor. Consequently, under optimal conditions, the designed aptasensor exhibited a lower detection limit of 0.05 pM and wide dynamic linear range from 0.15 pM to 40 nM for TB detection. Additionally, the proposed mediator-free and signal-amplified electrochemical aptasensor showed great potential in portable and cost-effective TB sensing devices. Copyright © 2013 Elsevier B.V. All rights reserved.

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)

Etude aerodynamique d'un jet turbulent impactant une paroi concave

NASA Astrophysics Data System (ADS)

LeBlanc, Benoit

Etant donne la demande croissante de temperatures elevees dans des chambres de combustion de systemes de propulsions en aerospatiale (turbomoteurs, moteur a reaction, etc.), l'interet dans le refroidissement par jets impactant s'est vu croitre. Le refroidissement des aubes de turbine permet une augmentation de temperature de combustion, ce qui se traduit en une augmentation de l'efficacite de combustion et donc une meilleure economie de carburant. Le transfert de chaleur dans les au bages est influence par les aspects aerodynamiques du refroidissement a jet, particulierement dans le cas d'ecoulements turbulents. Un manque de comprehension de l'aerodynamique a l'interieur de ces espaces confinees peut mener a des changements de transfert thermique qui sont inattendus, ce qui augmente le risque de fluage. Il est donc d'interet pour l'industrie aerospatiale et l'academie de poursuivre la recherche dans l'aerodynamique des jets turbulents impactant les parois courbes. Les jets impactant les surfaces courbes ont deja fait l'objet de nombreuses etudes. Par contre des conditions oscillatoires observees en laboratoire se sont averees difficiles a reproduire en numerique, puisque les structures d'ecoulements impactants des parois concaves sont fortement dependantes de la turbulence et des effets instationnaires. Une etude experimentale fut realisee a l'institut PPRIME a l'Universite de Poitiers afin d'observer le phenomene d'oscillation dans le jet. Une serie d'essais ont verifie les conditions d'ecoulement laminaires et turbulentes, toutefois le cout des essais experimentaux a seulement permis d'avoir un apercu du phenomene global. Une deuxieme serie d'essais fut realisee numeriquement a l'Universite de Moncton avec l'outil OpenFOAM pour des conditions d'ecoulement laminaire et bidimensionnel. Cette etude a donc comme but de poursuivre l'enquete de l'aerodynamique oscillatoire des jets impactant des parois courbes, mais pour un regime d'ecoulement transitoire, turbulent

2016 CEC Annual Workshop on Electrochemistry

DTIC Science & Technology

2016-08-31

Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 electrochemistry, electrolytes, lithium - ion batteries , electron transfer REPORT...the following topics: advanced electrolytes with applications, lithium - ion batteries , and electron transfer through films. CEC faculty members...11:40a-1:20p Lunch break. Lithium - ion Batteries Arumugam “Ram” Manthiram, Moderator 1:20-2:10p Steven J. Visco, PolyPlus Battery Company

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

Facilitating Conceptual Change in Students' Understanding of Electrochemistry.

ERIC Educational Resources Information Center

Niaz, Mansoor

2002-01-01

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

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…

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

PubMed

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

2004-08-20

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

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

PubMed

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

2014-11-01

Electrochemistry combined with (liquid chromatography) high resolution mass spectrometry was used to simulate the general reductive metabolism of three biologically important nitro aromatic molecules: 3-trifluoromethyl-4-nitrophenol (TFM), niclosamide, and nilutamide. TFM is a pesticide used in the Laurential Great Lakes while niclosamide and nilutamide are used in cancer therapy. At first, a flow-through electrochemical cell was directly connected to a high resolution mass spectrometer to evaluate the ability of electrochemistry to produce the main reduction metabolites of nitro aromatic, nitroso, hydroxylamine, and amine functional groups. Electrochemical experiments were then carried out at a constant potential of -2.5 V before analysis of the reduction products by LC-HRMS, which confirmed the presence of the nitroso, hydroxylamine, and amine species as well as dimers. Dimer identification illustrates the reactivity of the nitroso species with amine and hydroxylamine species. To investigate xenobiotic metabolism, the reactivity of nitroso species to biomolecules was also examined. Binding of the nitroso metabolite to glutathione was demonstrated by the observation of adducts by LC-ESI(+)-HRMS and the characteristics of their MSMS fragmentation. In conclusion, electrochemistry produces the main reductive metabolites of nitro aromatics and supports the observation of nitroso reactivity through dimer or glutathione adduct formation.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Creager, Stephen

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); electrochemicalmore » 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.« less

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

PubMed

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

2015-03-15

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

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

PubMed Central

Strelcov, Evgheni; Yang, Sang Mo; Jesse, Stephen; Balke, Nina; Vasudevan, Rama K.; Kalinin, Sergei V.

2016-01-01

Energy technologies of the 21st century require understanding and precise control over ion transport and electrochemistry at all length scales – from single atoms to macroscopic devices. This short review provides a summary of recent works dedicated to methods of advanced scanning probe microscopy for probing electrochemical transformations in solids at the meso-, nano- and atomic scales. Discussion presents advantages and limitations of several techniques and a wealth of examples highlighting peculiarities of nanoscale electrochemistry. PMID:27146961

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)

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.

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

NASA Astrophysics Data System (ADS)

Kurniawan, Rizmahardian Ashari; Kurniasih, Dedeh; Jukardi

2017-12-01

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

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

PubMed

Gindt, Yvonne M; Messyasz, Adriana; Jumbo, Pamela I

2015-05-12

VcCry1, a member of the CRY-DASH family, may serve two diverse roles in vivo, including blue-light signaling and repair of UV-damaged DNA. We have discovered that the electrochemistry of the flavin adenine dinucleotide cofactor of VcCry1 is locked to cycle only between the hydroquinone and neutral semiquinone states when UV-damaged DNA is present. Other potential substrates, including undamaged DNA and ATP, have no discernible effect on the electrochemistry, and the kinetics of the reduction is unaffected by damaged DNA. Binding of the damaged DNA substrate determines the role of the protein and prevents the presumed photochemistry required for blue-light signaling.

Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments

DOE PAGES

Genorio, Bostjan; Staszak-Jirkovský, Jakub; Assary, Rajeev S.; ...

2016-02-09

Efficient chemical transformations in energy conversion and storage systems depend on understanding superoxide anion (O 2 –) electrochemistry at atomic and molecular levels. Here, in this work, a combination of experimental and theoretical techniques are used for rationalizing, and ultimately understanding, the complexity of superoxide anion (electro)chemistry in organic environments. By exploring the O 2 + e – ↔ O 2 – reaction on well-characterized metal single crystals (Au, Pt, Ir), Pt single crystal modified with a single layer of graphene (Graphene@Pt(111)), and glassy carbon (GC) in 1,2 dimethoxyethane (DME) electrolytes, we demonstrate that (i) the reaction is an outer-spheremore » process; (ii) the reaction product O 2 – can “attack” any part of the DME molecule, i.e., the C–O bond via nucleophilic reaction and the C–H bond via radical hydrogen abstraction; (iii) the adsorption of carbon-based decomposition products and the extent of formation of a “solid electrolyte interface” (“SEI”) increases in the same order as the reactivity of the substrate, i.e., Pt(hkl)/Ir(hkl) » Au(hkl)/GC > Gaphene@Pt(111); and (iv) the formation of the “SEI” layer leads to irreversible superoxide electrochemistry on Pt(hkl) and Ir(hkl) surfaces. In conclusion, we believe this fundamental insight provides a pathway for the rational design of stable organic solvents that are urgently needed for the development of a new generation of reliable and affordable battery systems.« less

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. Copyright © 2013 Elsevier B.V. All rights reserved.

Etude theorique des fluctuations structurales dans les composes organiques a dimensionnalite reduite

NASA Astrophysics Data System (ADS)

Dumoulin, Benoit

Les systemes a dimensionnalite reduite constituent maintenant une branche entiere de la physique de la matiere condensee. Cette derniere s'est developpee rapidement au cours des dernieres annees, avec la decouverte des materiaux organiques qui presentent, justement, des proprietes physiques fortement anisotropes. Cette these presente une etude en trois parties de plusieurs composes organiques qui, bien que tres differents du point de vue de leurs compositions chimiques et de leurs proprietes physiques a haute temperature, subissent tous une instabilite structurale a tres basse temperature. De plus, dans chacun des cas, l'instabilite structurale est precedee d'un important regime fluctuatif a partir duquel les proprietes physiques changent de maniere significative. Notre etude suit un ordre chronologique inverse puisque nous nous attardons en premier lieu au cas de composes recemment decouverts: les composes de la famille des (BCPTTF)2X (X = PF6 , AsF6). Ces derniers sont des isolants magnetiques a la temperature ambiante et subissent une instabilite structurale de type spin-Peierls a une temperature appelee TSP. En particulier, nous nous interessons a l'etude des proprietes physiques de ces systemes dans le regime fluctuatif, qui precede cette instabilite. Notre etude theorique nous permet de comprendre en detail comment ces systemes s'approchent de l'instabilite struturale. Dans la seconde partie de cette these, nous etudions le regime fluctuatif (pre-transitionnel) observe experimentalement dans le compose de (TMTTF)2PF6. Ce compose organique, dont la structure s'apparente aux sels de Bechgaard, subit une instabilite de type spin-Peierls a une temperature T SP = 19K. Bien que ce compose possede la particularite d'etre un bon conducteur a la temperature ambiante, il subit une transition de type Mott-Hubbard a une temperature Trho ≈ 220K et devient alors un isolant magnetique, analogue aux composes de la famille des (BCPTTF)2X. Le regime fluctuatif precedant l

Electrochemistry of Some New Alkaline Battery Electrodes

DTIC Science & Technology

1976-02-01

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

Teaching Electrochemistry in the General Chemistry Laboratory through Corrosion Exercises

ERIC Educational Resources Information Center

Sanders, Richard W.; Crettol, Gregory L.; Brown, Joseph D.; Plummer, Patrick T.; Schendorf, Tara M.; Oliphant, Alex; Swithenbank, Susan B.; Ferrante, Robert F.; Gray, Joshua P.

2018-01-01

Electrochemistry is primarily taught in first-year undergraduate courses through batteries; this lab focuses instead on corrosion to apply electrochemical concepts of electrolytes, standard reduction potentials, galvanic cells, and other chemistry concepts including Le Chatelier's Principle and Henry's Law. Students investigate galvanic corrosion…

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

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.

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

PubMed

Hunter

1999-01-01

The Etude music magazine, founded by Theodore Presser, was one of a number of popular music magazines published in the years prior to the establishment of the music therapy profession in 1950. During its publication run from 1883 to 1957, over 100 music therapy related articles appeared, including 13 on the health benefits of singing published between 1891 and 1949. Written by authors with diverse backgrounds, such as the famous Battle Creek, Michigan physician John Harvey Kellogg and Boston music critic Louis C. Elson, the articles contained consistent and adamant support regarding the health benefits of singing. The advantages described were both physical and psychological, and were recommended prophylactically for well persons and therapeutically for ill persons. Although the articles varied in perspective, from philosophical to theoretical to pedagogical, there is a consistent holistic medicine theme that appeared almost ahead of its time and no doubt linked to the push for vocal music education in that era. The importance of The Etude in promulgating ideas that helped shape the early practice of music therapy should not be underestimated. For much of its publication run The Etude was the largest music periodical in print, reaching its peak circulation of 250,000 copies per month in 1924.

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…

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kelly, James J.; Goods, Steven Howard

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 frommore » within Sandia.« less

Cobalt-cadmium bimetallic porphyrin coordination polymers for electrochemistry application

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Enzymatic Activity Detection via Electrochemistry for Enceladus

NASA Technical Reports Server (NTRS)

Studemeister, Lucy; Koehne, Jessica; Quinn, Richard

2017-01-01

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

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.

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…

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

PubMed

Bartošík, M; Ondroušková, E

Cytosine methylation in DNA is an epigenetic mechanism regulating gene expression and plays a vital role in cell differentiation or proliferation. Tumor cells often exhibit aberrant DNA methylation, e.g. hypermethylation of tumor suppressor gene promoters. New methods, capable of determining methylation status of specific DNA sequences, are thus being developed. Among them, MS-HRM (methylation-specific high resolution melting) and electrochemistry offer relatively inexpensive instrumentation, fast assay times and possibility of screening multiple samples/DNA regions simultaneously. MS-HRM is due to its sensitivity and simplicity an interesting alternative to already established techniques, including methylation-specific PCR or bisulfite sequencing. Electrochemistry, when combined with suitable electroactive labels and electrode surfaces, has been applied in several unique strategies for discrimination of cytosines and methylcytosines. Both techniques were successfully tested in analysis of DNA methylation within promoters of important tumor suppressor genes and could thus help in achieving more precise diagnostics and prognostics of cancer. Aberrant methylation of promoters has already been described in hundreds of genes associated with tumorigenesis and could serve as important biomarker if new methods applicable into clinical practice are sufficiently advanced.Key words: DNA methylation - 5-methylcytosine - HRM analysis - melting temperature - DNA duplex - electrochemistry - nucleic acid hybridizationThis work was supported by MEYS - NPS I - LO1413.The authors declare they have no potential conflicts of interest concerning drugs, products, or services used in the study.The Editorial Board declares that the manuscript met the ICMJE recommendation for biomedical papers.Submitted: 6. 5. 2016Accepted: 16. 5. 2016.

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.

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

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

Layered transition metal dichalcogenide electrochemistry: journey across the periodic table.

PubMed

Chia, Xinyi; Pumera, Martin

2018-06-08

Studies on layered transition metal dichalcogenides (TMDs), in particular for Group VIB TMDs like MoS2 and WS2, have long reached a crescendo in the realms of electrochemical applications initiated by their remarkable catalytic and electronic properties. One area that garnered considerable attention is the fervent pursuit of layered TMDs as electrocatalysts for hydrogen evolution reaction (HER), driven by global efforts towards reducing carbon footprint and attaining hydrogen economy. This Tutorial Review captures the essence of electrochemistry of different classes of layered TMDs and metal chalcogenides across the period table and showcases their tuneable electrochemical and HER catalytic attributes that are governed by the elemental composition, structure and anisotropy. Of interest to the assiduously studied Group VIB TMDs, we describe the role of elemental constituents and material purity in aspects of surface composition and structure, on their electrochemistry. Across families of layered TMDs in the periodic table, we highlight the apparent trends in their electrochemical and electrocatalytic properties through diligent comparison. Inevitably, these trends vary according to the type of chalcogen or transition metal that constitutes the eventual TMD. Beyond layered TMDs, we discuss the electrochemistry and recent progress in HER electrocatalysis of other layered metal chalcogenides that are overshadowed by the success of Group VIB TMDs. At the pinnacle of the emergent applications of layered TMDs, it is prudent to demystify the intrinsic electrochemical behaviour that originates from the participation of the elemental constitution of transition metal or chalcogen. Moreover, knowledge of the catalytic and electronic properties of the various TMD families and emerging trends across the period or down the group is of paramount importance when introducing or refining their prospective uses. The annotations in this Tutorial Review are envisioned to promote

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

Membrane-entrapped microperoxidase as a 'solid-state' promoter in the electrochemistry of soluble metalloproteins.

PubMed Central

Brunori, M; Santucci, R; Campanella, L; Tranchida, G

1989-01-01

Immobilization of biological systems in solid matrices is presently of great interest, in view of the many potential advantages associated with both the higher stability of the immobilized macromolecules and the potential utilization for biotechnology. In the present paper the electrochemical behaviour of the undecapeptide from cytochrome c (called microperoxidase) tightly entrapped in cellulose triacetate membrane is reported; its utilization as 'solid-state' promoter in the electrochemistry of soluble metalloproteins is presented. The results obtained indicate that: (i) membrane-entrapped microperoxidase undergoes rapid reversible electron transfer at a glassy carbon electrode; (ii) the electrochemical process is diffusion-controlled; (iii) entrapped microperoxidase acts as 'solid-state' promoter in the electrochemistry of soluble cytochrome c and of azurin. PMID:2557833

DNA Electrochemistry and Electrochemical Sensors for Nucleic Acids.

PubMed

Ferapontova, Elena E

2018-06-12

Sensitive, specific, and fast analysis of nucleic acids (NAs) is strongly needed in medicine, environmental science, biodefence, and agriculture for the study of bacterial contamination of food and beverages and genetically modified organisms. Electrochemistry offers accurate, simple, inexpensive, and robust tools for the development of such analytical platforms that can successfully compete with other approaches for NA detection. Here, electrode reactions of DNA, basic principles of electrochemical NA analysis, and their relevance for practical applications are reviewed and critically discussed.

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

NASA Astrophysics Data System (ADS)

Acar Sesen, Burcin; Tarhan, Leman

2013-02-01

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 = 30) and control groups ( N = 32). The experimental group was taught using inquiry-based laboratory activities developed by the researchers and the control group was instructed using traditional laboratory activities. The results of the study indicated that instruction based on inquiry-based laboratory activities caused a significantly better acquisition of scientific concepts related to electrochemistry, and produced significantly higher positive attitudes towards chemistry and laboratory. In the light of the findings, it is suggested that inquiry-based laboratory activities should be developed and applied to promote students' understanding in chemistry subjects and to improve their positive attitudes.

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

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. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

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

PubMed

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

2013-11-01

Hematocrit (HCT) is known to be a confounding factor that interferes with many blood glucose (BG) measurement technologies, resulting in wrong readings. Dynamic electrochemistry has been identified as one possible way to correct for these potential deviations. The purpose of this laboratory investigation was to assess the HCT stability of four BG meters known to employ dynamic electrochemistry (BGStar and iBGStar, Sanofi; Wavesense Jazz, AgaMatrix; Wellion Linus, MedTrust) in comparison with three other devices (GlucoDock, Medisana; OneTouch Verio Pro, LifeScan; FreeStyle Freedom InsuLinx, Abbott-Medisense). Venous heparinized blood was immediately aliquoted after draw and manipulated to contain three different BG concentrations (60-90, 130-160, and 280-320 mg/dl) and five different HCT levels (25%, 35%, 45%, 55%, and 60%). After careful oxygenation to normal blood oxygen pressure, each of the resulting 15 different samples was measured six times with three devices and three strip lots of each meter. The YSI Stat 2300 served as laboratory reference method. Stability to HCT influence was assumed when less than 10% difference occurred between the highest and lowest mean glucose deviations in relation to HCT concentrations [hematocrit interference factor (HIF)]. Five of the investigated self-test meters showed a stable performance with the different HCT levels tested in this investigation: BGStar (HIF 4.6%), iBGStar (6.6%), Wavesense Jazz (4.1%), Wellion Linus (8.5%), and OneTouch Verio Pro (6.2%). The two other meters were influenced by HCT (FreeStyle InsuLinx 17.8%; GlucoDock 46.5%). In this study, meters employing dynamic electrochemistry, as used in the BGStar and iBGStar devices, were shown to correct for potential HCT influence on the meter results. Dynamic electrochemistry appears to be an effective way to handle this interfering condition. © 2013 Diabetes Technology Society.

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

PubMed Central

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

2013-01-01

Background Hematocrit (HCT) is known to be a confounding factor that interferes with many blood glucose (BG) measurement technologies, resulting in wrong readings. Dynamic electrochemistry has been identified as one possible way to correct for these potential deviations. The purpose of this laboratory investigation was to assess the HCT stability of four BG meters known to employ dynamic electrochemistry (BGStar and iBGStar, Sanofi; Wavesense Jazz, AgaMatrix; Wellion Linus, MedTrust) in comparison with three other devices (GlucoDock, Medisana; OneTouch Verio Pro, LifeScan; FreeStyle Freedom InsuLinx, Abbott-Medisense). Methods Venous heparinized blood was immediately aliquoted after draw and manipulated to contain three different BG concentrations (60–90, 130–160, and 280–320 mg/dl) and five different HCT levels (25%, 35%, 45%, 55%, and 60%). After careful oxygenation to normal blood oxygen pressure, each of the resulting 15 different samples was measured six times with three devices and three strip lots of each meter. The YSI Stat 2300 served as laboratory reference method. Stability to HCT influence was assumed when less than 10% difference occurred between the highest and lowest mean glucose deviations in relation to HCT concentrations [hematocrit interference factor (HIF)]. Results Five of the investigated self-test meters showed a stable performance with the different HCT levels tested in this investigation: BGStar (HIF 4.6%), iBGStar (6.6%), Wavesense Jazz (4.1%), Wellion Linus (8.5%), and OneTouch Verio Pro (6.2%). The two other meters were influenced by HCT (FreeStyle InsuLinx 17.8%; GlucoDock 46.5%). Conclusions In this study, meters employing dynamic electrochemistry, as used in the BGStar and iBGStar devices, were shown to correct for potential HCT influence on the meter results. Dynamic electrochemistry appears to be an effective way to handle this interfering condition. PMID:24351179

Ferrocene-pyrimidine conjugates: Synthesis, electrochemistry, physicochemical properties and antiplasmodial activities.

PubMed

Chopra, Rakesh; de Kock, Carmen; Smith, Peter; Chibale, Kelly; Singh, Kamaljit

2015-07-15

The promise of hybrid antimalarial agents and the precedence set by the antimalarial drug ferroquine prompted us to design ferrocene-pyrimidine conjugates. Herein, we report the synthesis, electrochemistry and anti-plasmodial evaluation of ferrocenyl-pyrimidine conjugates against chloroquine susceptible NF54 strain of the malaria parasite Plasmodium falciparum. Also their physicochemical properties have been studied. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

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

PubMed

Pakapongpan, Saithip; Poo-Arporn, Rungtiva P

2017-07-01

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

Effect of Cooperative Learning Strategies on Students' Understanding of Concepts in Electrochemistry

ERIC Educational Resources Information Center

Acar, Burcin; Tarhan, Leman

2007-01-01

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

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.

Computer-Animated Instruction and Students' Conceptual Change in Electrochemistry: Preliminary Qualitative Analysis

ERIC Educational Resources Information Center

Talib, Othman; Matthews, Robert; Secombe, Margaret

2005-01-01

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

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 =…

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lines, Amanda M.; Adami, Susan R.; Casella, Amanda J.

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eshghinejad, Ahmadreza; Nasr Esfahani, Ehsan; Wang, Peiqi

2016-05-28

Conventional electrochemical characterization techniques based on voltage and current measurements only probe faradaic and capacitive rates in aggregate. In this work we develop a scanning thermo-ionic microscopy (STIM) to probe local electrochemistry at the nanoscale, based on imaging of Vegard strain induced by thermal oscillation. It is demonstrated from both theoretical analysis and experimental validation that the second harmonic response of thermally induced cantilever vibration, associated with thermal expansion, is present in all solids, whereas the fourth harmonic response, caused by local transport of mobile species, is only present in ionic materials. The origin of STIM response is further confirmedmore » by its reduced amplitude with respect to increased contact force, due to the coupling of stress to concentration of ionic species and/or electronic defects. The technique has been applied to probe Sm-doped Ceria and LiFePO{sub 4}, both of which exhibit higher concentrations of mobile species near grain boundaries. The STIM gives us a powerful method to study local electrochemistry with high sensitivity and spatial resolution for a wide range of ionic systems, as well as ability to map local thermomechanical response.« less

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

ERIC Educational Resources Information Center

Tarkin, Aysegul; Uzuntiryaki-Kondakci, Esen

2017-01-01

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

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

PubMed Central

2016-01-01

The methylthiotransferases (MTTases) represent a subfamily of the S-adenosylmethionine (AdoMet) radical superfamily of enzymes that catalyze the attachment of a methylthioether (-SCH3) moiety on unactivated carbon centers. These enzymes contain two [4Fe-4S] clusters, one of which participates in the reductive fragmentation of AdoMet to generate a 5′-deoxyadenosyl 5′-radical and the other of which, termed the auxiliary cluster, is believed to play a central role in constructing the methylthio group and attaching it to the substrate. Because the redox properties of the bound cofactors within the AdoMet radical superfamily are so poorly understood, we have examined two MTTases in parallel, MiaB and RimO, using protein electrochemistry. We resolve the redox potentials of each [4Fe-4S] cluster, show that the auxiliary cluster has a potential higher than that of the AdoMet-binding cluster, and demonstrate that upon incubation of either enzyme with AdoMet, a unique low-potential state of the enzyme emerges. Our results are consistent with a mechanism whereby the auxiliary cluster is transiently methylated during substrate methylthiolation. PMID:27598886

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Materials and Manufacturing Challenges of Direct Methanol Fuel Cells

DTIC Science & Technology

2009-04-27

SPSf. Figure 5 shows four basic polymers in which benzimidazole (BIm), amino- benzimidazole (ABIm), nitrobenzimidazole (NBIm), and perimidine (PImd...Membranes Based on Sulfonated Polyetheretherketone and Polysulfone Bearing Benzimidazole Side Groups for Fuel Cells,” Electrochemistry Communications...Bearing Benzimidazole Side Groups for Direct Methanol Fuel Cells,” Electrochemical and Solid State Letters, Vol. 10, 2007, p. B70-B73. [12] Fu, Y.-Z

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

PubMed

Wang, Ting; Wang, Lu; Tu, Jiaojiao; Xiong, Huayu; Wang, Shengfu

2013-12-01

The direct electrochemistry and electrocatalysis of heme proteins entrapped in carbon-coated nickel magnetic nanoparticle-chitosan-dimethylformamide (CNN-CS-DMF) composite films were investigated in the hydrophilic ionic liquid [bmim][BF4]. The surface morphologies of a representative set of films were characterised via scanning electron microscopy. The proteins immobilised in the composite films were shown to retain their native secondary structure using UV-vis spectroscopy. The electrochemical performance of the heme proteins-CNN-CS-DMF films was evaluated via cyclic voltammetry and chronoamperometry. A pair of stable and well-defined redox peaks was observed for the heme protein films at formal potentials of -0.151 V (HRP), -0.167 V (Hb), -0.155 V (Mb) and -0.193 V (Cyt c) in [bmim][BF4]. Moreover, several electrochemical parameters of the heme proteins were calculated by nonlinear regression analysis of the square-wave voltammetry. The addition of CNN significantly enhanced not only the electron transfer of the heme proteins but also their electrocatalytic activity toward the reduction of H2O2. Low apparent Michaelis-Menten constants were obtained for the heme protein-CNN-CS-DMF films, demonstrating that the biosensors have a high affinity for H2O2. In addition, the resulting electrodes displayed a low detection limit and improved sensitivity for detecting H2O2, which indicates that the biocomposite film can serve as a platform for constructing new non-aqueous biosensors for real detection. Copyright © 2013 Elsevier B.V. All rights reserved.

Characterization of solution-phase and gas-phase reactions in on-line electrochemistry-thermospray tandem mass spectrometry.

PubMed

Volk, K J; Yost, R A; Brajter-Toth, A

1989-07-14

Electrochemistry was used on-line with high-performance liquid chromatography-thermospray tandem mass spectrometry to provide insight into the solution-phase decomposition reactions of electrochemically generated oxidation products. Products formed during electrooxidation were monitored as the electrode potential was varied. The solution reactions which follow the initial electron transfer at the electrode are affected by the vaporizer tip temperature of the thermospray probe and the composition of the thermospray buffer. Either hydrolysis or ammonolysis reactions of the initial electrochemical oxidation products can occur with pH 7 ammonium acetate buffer. Both the electrochemically generated and the synthesized disulfide of 6-thiopurine decompose under thermospray conditions to produce 6-thiopurine and purine-6-sulfinate. Solution-phase studies indicate that nucleophilic and electrophilic substitution reactions with purine-6-sulfinate result in the formation of purine, adenine, and hypoxanthine. Products were identified and characterized by tandem mass spectrometry. This work shows the first example of high-performance liquid chromatography used on-line with electrochemistry to separate stable oxidation products prior to analysis by thermospray tandem mass spectrometry. In addition, solution-phase and gas-phase studies with methylamine show that the site of the nucleophilic and electrophilic reactions is probably inside the thermospray probe. Most importantly, these results also show that the on-line combination of electrochemistry with thermospray tandem mass spectrometry provides valuable information about redox and associated chemical reactions of biological molecules such as the structures of intermediates or products as well as providing insight into reaction pathways.

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.

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

The Pre-exponential Factor in Electrochemistry.

PubMed

He, Zheng-Da; Chen, Yan-Xia; Santos, Elizabeth; Schmickler, Wolfgang

2018-07-02

Like many branches of science, not to mention culture in general, electrochemistry has a number of recurring topics: Areas of research that are popular for a certain time, then fade away as their possibilities seem to have been exhausted, only to return decades later as progress in experimental or theoretical techniques offer new possibilities for their investigation. A prime example are fuel cells, which have undergone five such cycles, but here we discuss a general concept of kinetics-the pre-exponential factor of a rate constant-which has undergone two such cycles. The first cycle was in the 1950-1980s, when the methods of electrochemical kinetics were developed, and the interpretation was based on transition-state theory. The second was triggered by the re-discovery of Kramers theory for reactions in condensed phases. This Minireview will show that the time has come for a third cycle based on recent progress in electrocatalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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…

Li/Ag 2VO 2PO 4 batteries: the roles of composite electrode constituents on electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2016-11-01

Silver vanadium phosphorous oxide, Ag 2V 2OPO 4, 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.

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.

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…

A Preliminary Study of Some of the Learning and Assessment Difficulties in Connection with O-Level Electrochemistry.

ERIC Educational Resources Information Center

Hillman, R. A. H.; And Others

1981-01-01

Describes a study which explored some difficulties related to technical and nontechnical vocabulary and the structure of the examination questions in electrochemistry. Includes results from a sample of 1,500 students in the fourth forms. (DS)

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poyraz, Altug S.; Huang, Jianping; Zhang, Bingjie

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

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…

Electrochemistry of Cytochrome P450 BM3 in Sodium Dodecyl Sulfate Films

PubMed Central

Udit, Andrew K.; Hill, Michael G.; Gray, Harry B.

2008-01-01

Direct electrochemistry of the cytochrome P450 BM3 heme domain (BM3) was achieved by confining the protein within sodium dodecyl sulfate (SDS) films on the surface of basal-plane graphite (BPG) electrodes. Cyclic voltammetry revealed the heme FeIII/II redox couple at −330 mV (vs. Ag/AgCl, pH 7.4). Up to 10 V/s, the peak current was linear with scan rate, allowing us to treat the system as surface-confined within this regime. The standard heterogeneous rate constant determined at 10 V/s was estimated to be 10 s−1. Voltammograms obtained for the BM3-SDS-BPG system in the presence of dioxygen exhibited catalytic waves at the onset of FeIII reduction. The altered heme reduction potential of the BM3-SDS-graphite system indicates that SDS is likely bound in the enzyme active-site region. Compared to other P450-surfactant systems, we find redox potentials and electron transfer rates that differ by ~ 100 mV and > 10-fold, respectively, indicating that the nature of the surfactant environment has a significant effect on the observed heme redox properties. PMID:17129070

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.

Common Principles of Molecular Electronics and Nanoscale Electrochemistry.

PubMed

Bueno, Paulo Roberto

2018-05-24

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

Introducing Students to Inner Sphere Electron Transfer Concepts through Electrochemistry Studies in Diferrocene Mixed-Valence Systems

ERIC Educational Resources Information Center

Ventura, Karen; Smith, Mark B.; Prat, Jacob R.; Echegoyen, Lourdes E.; Villagran´, Dino

2017-01-01

We have designed a 4 h physical chemistry laboratory to introduce upper division students to electrochemistry concepts, including mixed valency and electron transfer (ET), using cyclic and differential pulse voltammetries. In this laboratory practice, students use a ferrocene dimer consisting of two ferrocene centers covalently bonded through a…

Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lines, Amanda M.; Wang, Zheming; Clark, Sue B.

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 stabilizemore » 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.« less

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

NASA Astrophysics Data System (ADS)

O'Brien, Stephanie

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

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

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

PubMed

Yang, Sang Mo; Strelcov, Evgheni; Paranthaman, M Parans; Tselev, Alexander; Noh, Tae Won; Kalinin, Sergei V

2015-02-11

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

The use of bipolar electrochemistry in nanoscience: Contact free methods for the site selective modification of nanostructured carbon materials

NASA Astrophysics Data System (ADS)

Ndungu, Patrick Gathura

Bipolar electrochemistry occurs when an isolated conductive substrate inside an electric field supports both oxidation and reduction reactions. The method requires no direct contact between the power supply and the substrate. In the following thesis bipolar electrochemistry has been used to deposit palladium onto isolated graphite platelets, carbon nanofibers (CNF), and carbon nanotubes (CNT), as well as, various metals, a semiconductor, and an electropolymer on CNTs. Initial work used pulsed DC electric fields to deposit palladium onto isolated graphite platelets. Transmission electron microscopy (TEM) studies on the platelets found palladium metal on one area, indicative of a bipolar mechanism, and palladium deposits that varied from surface bound to highly ramified deposits. No correlation was found between the frequency used to prepare the deposits and the palladium metal dispersion. The same field intensities and frequencies used on the graphite platelets were used to produce CNFs with palladium on one tip. The amount of palladium deposited on one tip of a CNF was controlled by adjusting how long the electric field was applied. Preliminary experiments to produce bulk quantities of CNFs with palladium bipolar electrodeposits used CNFs ball milled with silica, and CNFs suspended in tetrahydrofuran or methylene chloride. The palladium content, measured by atomic absorption spectroscopy, of the functionalized CNFs in silica showed no difference with increased CNF loading; however, TEM studies found a small number of functionalized chloride used suspensions with high loadings of CNFs which led to small percentages of CNFs with bipolar electrodeposited palladium. Finally CNTs obtained commercially and CNTs grown using chemical vapor deposition were successfully functionalized using bipolar electrodeposition. These experiments demonstrate a reliable and controlled method to modify nanostructured materials.

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

ERIC Educational Resources Information Center

Lee, Tien Tien; Osman, Kamisah

2011-01-01

Electrochemistry is found to be a difficult topic to learn due to its abstract concepts that involve the macroscopic, microscopic and symbolic representation levels. Research showed that animation and simulation using Information and Communication Technology (ICT) can help students to visualize and hence enhance students' understanding in learning…

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

PubMed

Dochter, Alexandre; Garnier, Tony; Pardieu, Elodie; Chau, Nguyet Trang Thanh; Maerten, Clément; Senger, Bernard; Schaaf, Pierre; Jierry, Loïc; Boulmedais, Fouzia

2015-09-22

The development of new surface functionalization methods that are easy to use, versatile, and allow local deposition represents a real scientific challenge. Overcoming this challenge, we present here a one-pot process that consists in self-assembling, by electrochemistry on an electrode, films made of oppositely charged macromolecules. This method relies on a charge-shifting polyanion, dimethylmaleic-modified poly(allylamine) (PAHd), that undergoes hydrolysis at acidic pH, leading to an overall switching of its charge. When a mixture of the two polyanions, PAHd and poly(styrenesulfonate) (PSS), is placed in contact with an electrode, where the pH is decreased locally by electrochemistry, the transformation of PAHd into a polycation (PAH) leads to the continuous self-assembly of a nanometric PAH/PSS film by electrostatic interactions. The pH decrease is obtained by the electrochemical oxidation of hydroquinone, which produces protons locally over nanometric distances. Using a negatively charged enzyme, alkaline phosphatase (AP), instead of PSS, this one-pot process allows the creation of enzymatically active films. Under mild conditions, self-assembled PAH/AP films have an enzymatic activity which is adjustable simply by controlling the self-assembly time. The selective functionalization of microelectrode arrays by PAH/AP was achieved, opening the route toward miniaturized biosensors.

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

PubMed

Wigger, Tina; Seidel, Albrecht; Karst, Uwe

2017-06-01

Electrochemistry coupled to liquid chromatography and mass spectrometry was used for simulating the biological and environmental fate of polycyclic aromatic hydrocarbons (PAHs) as well as for studying the PAH degradation behavior during electrochemical remediation. Pyrene and benzo[a]pyrene were selected as model compounds and oxidized within an electrochemical thin-layer cell equipped with boron-doped diamond electrode. At potentials of 1.2 and 1.6 V vs. Pd/H 2 , quinones were found to be the major oxidation products for both investigated PAHs. These quinones belong to a large group of PAH derivatives referred to as oxygenated PAHs, which have gained increasing attention in recent years due to their high abundance in the environment and their significant toxicity. Separation of oxidation products allowed the identification of two pyrene quinone and three benzo[a]pyrene quinone isomers, all of which are known to be formed via photooxidation and during mammalian metabolism. The good correlation between electrochemically generated PAH quinones and those formed in natural processes was also confirmed by UV irradiation experiments and microsomal incubations. At potentials higher than 2.0 V, further degradation of the initial oxidation products was observed which highlights the capability of electrochemistry to be used as remediation technique. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

ERIC Educational Resources Information Center

Sen, Senol; Yilmaz, Ayhan; Geban, Ömer

2016-01-01

The purpose of this study was to investigate the effect of Process Oriented Guided Inquiry Learning (POGIL) method compared to traditional teaching method on 11th grade students' conceptual understanding of electrochemistry concepts. Participants were 115 students from a public school in Turkey. Nonequivalent control group design was used. Two…

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

PubMed

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

2016-11-01

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

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…

Synthesis of Copper Birnessite, Cu xMnO y·nH 2O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry

DOE PAGES

Li, Yue Ru; Marschilok, Amy C.; Takeuchi, Esther S.; ...

2015-11-24

This report describes the first detailed electrochemical examination of a series of copper birnessite samples under lithium-based battery conditions, allowing a structure/function analysis of the electrochemistry and related material properties. To obtain the series of copper birnessite samples, a novel synthetic approach for the preparation of copper birnessite, Cu xMnO y·nH 2O is reported. The copper content (x) in Cu xMnO y·nH 2O, 0.28 >= x >= 0.20, was inversely proportional to crystallite size, which ranged from 12 to 19 nm. The electrochemistry under lithium-based battery conditions showed that the higher copper content (x = 0.28) and small crystallite sizemore » (similar to 12 nm) sample delivered similar to 194 mAh/g, about 20% higher capacity than the low copper content (x = 0.22) and larger crystallite size (similar to 19 nm) material. In addition, Cu xMnO y·nH 2O displays quasi-reversible electrochemistry in magnesium based electrolytes, indicating that copper birnessite could be a candidate for future application in magnesium-ion batteries.« less

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.

Electrochemistry of sulfur and polysulfides in ionic liquids.

PubMed

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

2011-12-01

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

Bioconjugation of zirconium uridine monophosphate: application to myoglobin direct electrochemistry.

PubMed

Qiao, Yuanbiao; Jian, Fangfang; Bai, Qian

2008-03-14

Porous nano-granule of zirconium uridine monophosphate, Zr(UMP)2.H2O is, for the first time, synthesized under mild experimental conditions and applied to the bioconjugation of myoglobin (Mb) to realize its direct electron transfer. UV-vis and resonance Raman spectroscopies prove that Mb in the Zr(UMP)2.H2O film maintains its secondary structure similar to the native state. The conjugation film of the Mb-Zr(UMP)2.H2O on the glassy carbon (GC) electrode gives a well-defined and quasi-reversible cyclic voltammogram, which reflects the direct electron transfer of the heme Fe III/Fe II couple of Mb. On the basis of the satisfying bioelectrocatalysis of the nano-conjugation of Mb and genetic substrate, a kind of mediator-free biosensor for H2O2 is developed. The linear range for H2O2 detection is estimated to be 3.92-180.14 microM. The apparent Michaelis-Menten constant (Km) and the detection limit based on the signal-to-noise ratio of 3 are found to be 196.1 microM and 1.52 microM, respectively. Both the apparent Michaelis-Menten constant and the detection limit herein are much lower than currently reported values from other Mb films. This kind of sensor possesses excellent stability, long-term life (more than 20 days) and good reproducibility.

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,…

Electrochemistry of 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene ligands: free phosphines, metal complexes, and chalcogenides.

PubMed

Mandell, Chelsea L; Kleinbach, Shannon S; Dougherty, William G; Kassel, W Scott; Nataro, Chip

2010-10-18

The oxidative electrochemistries of a series of chiral bisphosphinoferrocene ligands, 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene (FerroTANE) and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene (FerroLANE), were examined. The reversibility of the oxidation is sensitive to the steric bulk of the alkyl groups. New transition metal compounds and phosphine chalcogenides of these ligands were prepared and characterized. X-ray crystal structures of 10 of these compounds are reported. The percent buried volume (%V(bur)) is a recently developed measurement based on crystallographic data that examines the steric bulk of N-heterocyclic carbene and phosphine ligands. The %V(bur) for the FerroTANE and FerroLANE structures with methyl or ethyl substituents suggests these ligands are similar in steric properties to 1,1'-bis(diphenylphosphino)ferrocene (dppf). In addition the %V(bur) has been found to correlate well with the Tolman cone angle for phosphine chalcogenides. The oxidative electrochemistries of the transition metal complexes occur at more positive potentials than the free ligands. While a similar positive shift is seen for the oxidative electrochemistries of the phosphine chalcogenides, the oxidation of the phosphine selenides does not occur at the iron center, but rather oxidation occurs at the selenium atoms.

Tungsten Oxides for Photocatalysis, Electrochemistry, and Phototherapy.

PubMed

Huang, Zhen-Feng; Song, Jiajia; Pan, Lun; Zhang, Xiangwen; Wang, Li; Zou, Ji-Jun

2015-09-23

The conversion, storage, and utilization of renewable energy have all become more important than ever before as a response to ever-growing energy and environment concerns. The performance of energy-related technologies strongly relies on the structure and property of the material used. The earth-abundant family of tungsten oxides (WOx ≤3 ) receives considerable attention in photocatalysis, electrochemistry, and phototherapy due to their highly tunable structures and unique physicochemical properties. Great breakthroughs have been made in enhancing the optical absorption, charge separation, redox capability, and electrical conductivity of WOx ≤3 through control of the composition, crystal structure, morphology, and construction of composite structures with other materials, which significantly promotes the efficiency of processes and devices based on this material. Herein, the properties and synthesis of WOx ≤3 family are reviewed, and then their energy-related applications are highlighted, including solar-light-driven water splitting, CO2 reduction, and pollutant removal, electrochromism, supercapacitors, lithium batteries, solar and fuel cells, non-volatile memory devices, gas sensors, and cancer therapy, from the aspect of function-oriented structure design and control. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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,…

Light Emission Mechanisms in CuInS 2 Quantum Dots Evaluated by Spectral Electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fuhr, Addis S.; Yun, Hyeong Jin; Makarov, Nikolay S.

Luminescent CuInS 2 (CIS) quantum dots (QDs) exhibit highly efficient intragap emission and long, hundreds-of-nanoseconds radiative lifetimes. These spectral properties, distinct from structurally similar II–VI QDs, can be explained by the involvement of intragap defect states containing a localized hole capable of coupling with a conduction band electron for a radiative transition. However, the absolute energies of the intragap and band-edge states, the structure of the emissive defect(s), and the role and origin of nonemissive decay channels still remain poorly understood. Here, we address these questions by applying methods of spectral electrochemistry. Cyclic voltammetry measurements reveal a well-defined intragap statemore » whose redox potential is close to that of the Cu x defect state (where x = 1+ or 2+). The energy offset of this state from the valence band accounts well for the apparent photoluminescence Stokes shift observed in optical spectra. These results provide direct evidence that Cu-related defects serve as emission centers responsible for strong intragap emission from CIS QDs. We then use in situ spectroelectrochemistry to reveal two distinct emission pathways based on the differing oxidation states of Cu defects, which can be controlled by altering QD stoichiometry (1+ for stoichiometric QDs and 2+ for Cu-deficient QDs).« less

Light Emission Mechanisms in CuInS 2 Quantum Dots Evaluated by Spectral Electrochemistry

DOE PAGES

Fuhr, Addis S.; Yun, Hyeong Jin; Makarov, Nikolay S.; ...

2017-09-07

Luminescent CuInS 2 (CIS) quantum dots (QDs) exhibit highly efficient intragap emission and long, hundreds-of-nanoseconds radiative lifetimes. These spectral properties, distinct from structurally similar II–VI QDs, can be explained by the involvement of intragap defect states containing a localized hole capable of coupling with a conduction band electron for a radiative transition. However, the absolute energies of the intragap and band-edge states, the structure of the emissive defect(s), and the role and origin of nonemissive decay channels still remain poorly understood. Here, we address these questions by applying methods of spectral electrochemistry. Cyclic voltammetry measurements reveal a well-defined intragap statemore » whose redox potential is close to that of the Cu x defect state (where x = 1+ or 2+). The energy offset of this state from the valence band accounts well for the apparent photoluminescence Stokes shift observed in optical spectra. These results provide direct evidence that Cu-related defects serve as emission centers responsible for strong intragap emission from CIS QDs. We then use in situ spectroelectrochemistry to reveal two distinct emission pathways based on the differing oxidation states of Cu defects, which can be controlled by altering QD stoichiometry (1+ for stoichiometric QDs and 2+ for Cu-deficient QDs).« less

Analysis of the electrochemistry of hemes with Ems spanning 800 mV

PubMed Central

Zheng, Zhong; Gunner, M. R.

2009-01-01

The free energy of heme reduction in different proteins is found to vary over more than 18 kcal/mol. It is a challenge to determine how proteins manage to achieve this enormous range of Ems with a single type of redox cofactor. Proteins containing 141 unique hemes of a-, b-, and c-type, with bis-His, His-Met, and aquo-His ligation were calculated using Multi-Conformation Continuum Electrostatics (MCCE). The experimental Ems range over 800 mV from −350 mV in cytochrome c3 to 450 mV in cytochrome c peroxidase (vs. SHE). The quantitative analysis of the factors that modulate heme electrochemistry includes the interactions of the heme with its ligands, the solvent, the protein backbone, and sidechains. MCCE calculated Ems are in good agreement with measured values. Using no free parameters the slope of the line comparing calculated and experimental Ems is 0.73 (R2 = 0.90), showing the method accounts for 73% of the observed Em range. Adding a +160 mV correction to the His-Met c-type hemes yields a slope of 0.97 (R2 = 0.93). With the correction 65% of the hemes have an absolute error smaller than 60 mV and 92% are within 120 mV. The overview of heme proteins with known structures and Ems shows both the lowest and highest potential hemes are c-type, whereas the b-type hemes are found in the middle Em range. In solution, bis-His ligation lowers the Em by ≈205 mV relative to hemes with His-Met ligands. The bis-His, aquo-His, and His-Met ligated b-type hemes all cluster about Ems which are ≈200 mV more positive in protein than in water. In contrast, the low potential bis-His c-type hemes are shifted little from in solution, whereas the high potential His-Met c-type hemes are raised by ≈300 mV from solution. The analysis shows that no single type of interaction can be identified as the most important in setting heme electrochemistry in proteins. For example, the loss of solvation (reaction field) energy, which raises the Em, has been suggested to be a major factor in

Conceptual Difficulties Experienced by Prospective Teachers in Electrochemistry: Half-Cell Potential, Cell Potential, and Chemical and Electrochemical Equilibrium in Galvanic Cells.

ERIC Educational Resources Information Center

Ozkaya, Ali Riza

2002-01-01

A previous study of prospective teachers found that students from different countries and different levels of electrochemistry hold common misconceptions, indicating that concepts were presented to them poorly. Reports on how prospective teachers' scientifically incorrect ideas were used to form assertion-reason-type questions and how these…

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

PubMed

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

2017-05-09

In this study, the electrochemical conversion of xylose to δ-valerolactone via carbonyl intermediates is demonstrated. The conversion was achieved in aqueous media and at ambient conditions. This study also demonstrates that the feedstock for production of renewable chemicals and biofuels through electrochemistry can be extended to primary carbohydrate molecules. This is the first report on a one-pot electrochemical deoxygenation of xylose to δ-valerolactone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

2018-01-01

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

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.

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

PubMed

Kabeshov, Mikhail A; Musio, Biagia; Murray, Philip R D; Browne, Duncan L; Ley, Steven V

2014-09-05

An expedient synthesis of the indole alkaloid nazlinine is reported. Judicious choice of flow electrochemistry as an enabling technology has permitted the rapid generation of a small library of unnatural relatives of this biologically active molecule. Furthermore, by conducting the key electrochemical Shono oxidation in a flow cell, the loading of electrolyte can be significantly reduced to 20 mol % while maintaining a stable, broadly applicable process.

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

PubMed

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

2017-02-05

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

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

NASA Astrophysics Data System (ADS)

Lee, Chiun-Chang; Ryham, Rolf J.

2018-04-01

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

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

PubMed Central

Maréchal, Amandine; Kido, Yasutoshi; Kita, Kiyoshi; Moore, Anthony L.; Rich, Peter R.

2009-01-01

Electrochemistry coupled with Fourier transform infrared (IR) spectroscopy was used to investigate the redox properties of recombinant alternative ubiquinol oxidase from Trypanosoma brucei, the organism responsible for African sleeping sickness. Stepwise reduction of the fully oxidized resting state of recombinant alternative ubiquinol oxidase revealed two distinct IR redox difference spectra. The first of these, signal 1, titrates in the reductive direction as an n = 2 Nernstian component with an apparent midpoint potential of 80 mV at pH 7.0. However, reoxidation of signal 1 in the same potential range under anaerobic conditions did not occur and only began with potentials in excess of 500 mV. Reoxidation by introduction of oxygen was also unsuccessful. Signal 1 contained clear features that can be assigned to protonation of at least one carboxylate group, further perturbations of carboxylic and histidine residues, bound ubiquinone, and a negative band at 1554 cm−1 that might arise from a radical in the fully oxidized protein. A second distinct IR redox difference spectrum, signal 2, appeared more slowly once signal 1 had been reduced. This component could be reoxidized with potentials above 100 mV. In addition, when both signals 1 and 2 were reduced, introduction of oxygen caused rapid oxidation of both components. These data are interpreted in terms of the possible active site structure and mechanism of oxygen reduction to water. PMID:19767647

Etude de faisabilite d'un systeme eolien diesel avec stockage d'air comprime

NASA Astrophysics Data System (ADS)

Benchaabane, Youssef

Le Systeme Hybride Eolien-Diesel avec Stockage d'Air Comprime (SHEDAC) utilise l'hybridation pneumatique pour remplacer la consommation des combustibles fossiles par de l'energie renouvelable, plus particulierement de l'energie eolienne. Le surplus de l'energie eolienne est utilise pour comprimer et stocker de l'air qui est utilise ensuite pour suralimenter le moteur diesel. Le memoire de maitrise est constitue de deux articles scientifiques. Le premier article presente le developpement d'un logiciel dedie a l'etude de faisabilite d'un systeme eolien-diesel avec stockage d'air comprime. Cette etude est basee sur l'analyse des couts et des revenus, des couts des equipements (eolienne, moteur diesel, systeme de stockage d'air). Elle est completee par une analyse de sensibilite aux differents parametres, une analyse des risques et des emissions des gaz a effet de serre (GES). Le deuxieme article est une application de ce logiciel pour l'installation d'un systeme SHEDAC au camp minier Esker au Quebec en remplacement des sources actuelles de production d'energie. L'utilisation du stockage d'air comprime a l'aide d'un systeme SHEDAC est le plus rentable par rapport a l'utilisation de l'energie eolienne seule ou d'une centrale thermique au diesel seule ou des deux combinees. Avec une valeur actuelle nette et un taux de rendement interne plus eleves, cette solution permet d'obtenir le plus bas cout de l'energie pour cette region eloignee. None None None

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abruna, Hector D.

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

Electrochemistry-Assisted Top-Down Characterization of Disulfide-Containing Proteins

PubMed Central

Zhang, Yun; Cui, Weidong; Zhang, Hao; Dewald, Howard D.; Chen, Hao

2013-01-01

Covalent disulfide bond linkage in a protein represents an important challenge for mass spectrometry (MS)-based top-down protein structure analysis as it reduces the backbone cleavage efficiency for MS/MS dissociation. This study presents a strategy for solving this critical issue via integrating electrochemistry (EC) online with top-down MS approach. In this approach, proteins undergo electrolytic reduction in an electrochemical cell to break disulfide bonds and then online ionized into gaseous ions for analysis by electron-capture dissociation (ECD) and collision-induced dissociation (CID). The electrochemical reduction of proteins allows to remove disulfide bond constraints and also leads to increased charge numbers of the resulting protein ions. As a result, sequence coverage was significantly enhanced, as exemplified by β-lactoglobulin A (24 vs. 73 backbone cleavages before and after electrolytic reduction, respectively) and lysozyme (5 vs. 66 backbone cleavages before and after electrolytic reduction, respectively). This methodology is fast and does not need chemical reductants, which would have an important impact in high-throughput proteomics research. PMID:22448817

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

PubMed

Zhang, Yun; Cui, Weidong; Zhang, Hao; Dewald, Howard D; Chen, Hao

2012-04-17

Covalent disulfide bond linkage in a protein represents an important challenge for mass spectrometry (MS)-based top-down protein structure analysis as it reduces the backbone cleavage efficiency for MS/MS dissociation. This study presents a strategy for solving this critical issue via integrating electrochemistry (EC) online with a top-down MS approach. In this approach, proteins undergo electrolytic reduction in an electrochemical cell to break disulfide bonds and then undergo online ionization into gaseous ions for analysis by electron-capture dissociation (ECD) and collision-induced dissociation (CID). The electrochemical reduction of proteins allows one to remove disulfide bond constraints and also leads to increased charge numbers of the resulting protein ions. As a result, sequence coverage was significantly enhanced, as exemplified by β-lactoglobulin A (24 vs 75 backbone cleavages before and after electrolytic reduction, respectively) and lysozyme (5 vs 66 backbone cleavages before and after electrolytic reduction, respectively). This methodology is fast and does not need chemical reductants, which would have an important impact in high-throughput proteomics research.

Electrochemistry at Edge of Single Graphene Layer in a Nanopore

PubMed Central

Banerjee, Shouvik; Shim, Jiwook; Rivera, Jose; Jin, Xiaozhong; Estrada, David; Solovyeva, Vita; You, Xiuque; Pak, James; Pop, Eric; Aluru, Narayana; Bashir, Rashid

2013-01-01

We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and Al2O3 dielectric layers. Nanopores, with diameters ranging from 5 to 20 nm, are formed by an electron beam sculpting process on the stacked layers. This leads to unique edge structure which, along with the atomically thin nature of the embedded graphene electrode, demonstrates electrochemical current densities as high as 1.2 × 104 A/cm2. The graphene edge embedded structure offers a unique capability to study the electrochemical exchange at an individual graphene edge, isolated from the basal plane electrochemical activity. We also report ionic current modulation in the nanopore by biasing the embedded graphene terminal with respect to the electrodes in the fluid. The high electrochemical specific current density for a graphene nanopore-based device can have many applications in sensitive chemical and biological sensing, and energy storage devices. PMID:23249127

Graphene oxide electrochemistry: the electrochemistry of graphene oxide modified electrodes reveals coverage dependent beneficial electrocatalysis

PubMed Central

Smith, Graham C.

2017-01-01

The modification of electrode surfaces is widely implemented in order to try and improve electron transfer kinetics and surface interactions, most recently using graphene related materials. Currently, the use of ‘as is’ graphene oxide (GO) has been largely overlooked, with the vast majority of researchers choosing to reduce GO to graphene or use it as part of a composite electrode. In this paper, ‘as is’ GO is explored and electrochemically characterized using a range of electrochemical redox probes, namely potassium ferrocyanide(II), N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD), dopamine hydrochloride and epinephrine. Furthermore, the electroanalytical efficacy of GO is explored towards the sensing of dopamine hydrochloride and epinephrine via cyclic voltammetry. The electrochemical response of GO is benchmarked against pristine graphene and edge plane-/basal plane pyrolytic graphite (EPPG and BPPG respectively) alternatives, where the GO shows an enhanced electrochemical/electroanalytical response. When using GO as an electrode material, the electrochemical response of the analytes studied herein deviate from that expected and exhibit altered electrochemical responses. The oxygenated species encompassing GO strongly influence and dominate the observed voltammetry, which is crucially coverage dependent. GO electrocatalysis is observed, which is attributed to the presence of beneficial oxygenated species dictating the response in specific cases, demonstrating potential for advantageous electroanalysis to be realized. Note however, that crucial coverage based regions are observed at GO modified electrodes, owing to the synergy of edge plane sites and oxygenated species. We report the true beneficial electrochemistry of GO, which has enormous potential to be beneficially used in various electrochemical applications ‘as is’ rather than be simply used as a precursor to making graphene and is truly a fascinating member of the graphene family. PMID

Hazard Studies for Solid Propellant Rocket Motors (Etude des Risque pour les Moteurs-Fusees a Propergols Solides)

DTIC Science & Technology

1990-09-01

RESEARCH AND DEVELOPMENT (ORGANISATION DU TRAITE DE LATIANTIOUF NORD) AGARDograph No.3 16 Hazard Studies for Solid Propellant Rocket Motors (Etudes de...member nations to use their research and development capabilities for the common benefit of the NATO community; - Providing scientific and technical...advice and assistance to the Military Committee in the field of aerospace research and development (with particular regard to its military application

Tunnel Structured α-MnO 2 with Different Tunnel Cations (H + , K + , Ag + ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry

DOE PAGES

Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo; ...

2017-07-12

α-MnO 2 type manganese dioxide is an interesting prospective cathode material for reversible lithium insertion owing to its cation accessible tunnels (0.46nm x 0.46nm), high voltage, and low cost. The tunneled structure is synthetically formed by the assistance of cations acting as structure directing agents where the cations may remain in the tunnel. The electrochemistry of this family of materials is strongly dependent on the morphological and physicochemical (i.e. surface area, crystallite size, and average manganese oxidation state) properties as well as tunnel occupancy. For this work, we prepared a set of materials Mn 8O 16·0.81H 2O, K 0.81Mn 8Omore » 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O with similar nanorod morphology, crystallite size, surface area, and tunnel water content. This set of samples allowed us to investigate the role of tunnel cations in the electrochemistry of α-MnO 2 type manganese dioxide in a lithium based environment while minimizing the effects of the other parameters. The electrochemistry was evaluated using cyclic voltammetry, galvanostatic cycling, rate capability, and galvanostatic intermittent titration type testing. Mn 8O 16·0.81H 2O showed higher loaded voltages, improved capacity retention, and higher specific energy relative to K 0.81Mn 8O 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O. After 100 cycles, Mn 8O 16·0.81H 2O delivered ~200% more capacity than Ag 1.33Mn 8O 16·0.95H 2O (64 vs. 129 mAh/g) and ~35% more capacity than K 0.81Mn 8O 16·0.78H 2O (85 vs. 129 mAh/g). Mn 8O 16·0.81H 2O also showed higher effective lithium diffusion coefficients (DLi+) and higher rate capability compared to K 0.81Mn 8O 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O suggesting faster Li+ ion diffusion in the absence of large metal tunnel cations.« less

Tunnel Structured α-MnO 2 with Different Tunnel Cations (H + , K + , Ag + ) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo

α-MnO 2 type manganese dioxide is an interesting prospective cathode material for reversible lithium insertion owing to its cation accessible tunnels (0.46nm x 0.46nm), high voltage, and low cost. The tunneled structure is synthetically formed by the assistance of cations acting as structure directing agents where the cations may remain in the tunnel. The electrochemistry of this family of materials is strongly dependent on the morphological and physicochemical (i.e. surface area, crystallite size, and average manganese oxidation state) properties as well as tunnel occupancy. For this work, we prepared a set of materials Mn 8O 16·0.81H 2O, K 0.81Mn 8Omore » 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O with similar nanorod morphology, crystallite size, surface area, and tunnel water content. This set of samples allowed us to investigate the role of tunnel cations in the electrochemistry of α-MnO 2 type manganese dioxide in a lithium based environment while minimizing the effects of the other parameters. The electrochemistry was evaluated using cyclic voltammetry, galvanostatic cycling, rate capability, and galvanostatic intermittent titration type testing. Mn 8O 16·0.81H 2O showed higher loaded voltages, improved capacity retention, and higher specific energy relative to K 0.81Mn 8O 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O. After 100 cycles, Mn 8O 16·0.81H 2O delivered ~200% more capacity than Ag 1.33Mn 8O 16·0.95H 2O (64 vs. 129 mAh/g) and ~35% more capacity than K 0.81Mn 8O 16·0.78H 2O (85 vs. 129 mAh/g). Mn 8O 16·0.81H 2O also showed higher effective lithium diffusion coefficients (DLi+) and higher rate capability compared to K 0.81Mn 8O 16·0.78H 2O and Ag 1.33Mn 8O 16·0.95H 2O suggesting faster Li+ ion diffusion in the absence of large metal tunnel cations.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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.more » 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.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 alsomore » proposed.« less

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

Structure and electrochemistry of proteins harboring iron-sulfur clusters of different nuclearities. Part II. [4Fe-4S] and [3Fe-4S] iron-sulfur proteins.

PubMed

Zanello, Piero

2018-06-01

In the context of the plethora of proteins harboring iron-sulfur clusters we have already reviewed structure/electrochemistry of metalloproteins expressing single types of iron-sulfur clusters (namely: {Fe(Cys) 4 }, {[Fe 2 S 2 ](Cys) 4 }, {[Fe 2 S 2 ](Cys) 3 (X)} (X = Asp, Arg, His), {[Fe 2 S 2 ](Cys) 2 (His) 2 }, {[Fe 3 S 4 ](Cys) 3 }, {[Fe 4 S 4 ](Cys) 4 } and {[Fe 4 S 4 ](S γ Cys ) 3 (nonthiolate ligand)} cores) and their synthetic analogs. More recently we are focussing on structure/electrochemistry of metalloproteins harboring iron-sulfur centres of different nuclearities. Having started such a subject with proteins harboring [4Fe-4S] and [2Fe-2S] clusters, we now depict the state of art of proteins containing [4Fe-4S] and [3Fe-4S] clusters. Copyright © 2018 Elsevier Inc. All rights reserved.

Magnesium-ion battery-relevant electrochemistry of MgMn 2O 4: crystallite size effects and the notable role of electrolyte water content

DOE PAGES

Yin, Jiefu; Brady, Alexander B.; Takeuchi, Esther S.; ...

2017-03-06

MgMn 2O 4 nanoparticles with crystallite sizes of 11 (MMO-1) and 31 nm (MMO-2) were synthesized and their magnesium-ion battery-relevant electrochemistry was investigated. Here, MMO-1 delivered an initial capacity of 220 mA h g –1 (678 mW h g –1). Electrolyte water content had a profound effect on cycle retention.

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.

Li/Ag 2VO 2PO 4 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, Ag 2VO 2PO 4, 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: Ag 2VO 2PO 4 only, Ag 2VO 2PO 44 with binder, and Ag 2VOmore » 2PO 4 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 Ag 0. Ex situ XRD and EXAFS modeling were used to quantify the amount of Ag 0 formed. Results indicate that the metal center reduced (V 5+ or Ag +) was highly dependent on composite composition (presence of PTFE, carbon), depth of discharge (Ag 0 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 Ag 0. Lastly, this study provides insight into the factors controlling the electrochemistry of resistive active materials in composite electrodes.« less

Li/Ag 2VO 2PO 4 batteries: the roles of composite electrode constituents on electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

In this study, we utilize silver vanadium phosphorous oxide, Ag 2VO 2PO 4, 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: Ag 2VO 2PO 4 only, Ag 2VO 2PO 44 with binder, and Ag 2VOmore » 2PO 4 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 Ag 0. Ex situ XRD and EXAFS modeling were used to quantify the amount of Ag 0 formed. Results indicate that the metal center reduced (V 5+ or Ag +) was highly dependent on composite composition (presence of PTFE, carbon), depth of discharge (Ag 0 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 Ag 0. Lastly, this study provides insight into the factors controlling the electrochemistry of resistive active materials in composite electrodes.« less

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

PubMed

Taşdemir, Hüdai I; Kiliç, E

2014-09-01

The electrochemistry of moexipril (MOE) was studied by electrochemical methods with theoretical calculations performed at B3LYP/6-31 + G (d)//AM1. Cyclic voltammetric studies were carried out based on a reversible and adsorption-controlled reduction peak at -1.35 V on a hanging mercury drop electrode (HMDE). Concurrently irreversible diffusion-controlled oxidation peak at 1.15 V on glassy carbon electrode (GCE) was also employed. Potential values are according to Ag/AgCI, (3.0 M KCI) and measurements were performed in Britton-Robinson buffer of pH 5.5. Tentative electrode mechanisms were proposed according to experimental results and ab-initio calculations. Square-wave adsorptive stripping voltammetric methods have been developed and validated for quantification of MOE in pharmaceutical preparations. Linear working range was established as 0.03-1.35 microM for HMDE and 0.2-20.0 microM for GCE. Limit of quantification (LOQ) was calculated to be 0.032 and 0.47 microM for HMDE and GCE, respectively. Methods were successfully applied to assay the drug in tablets by calibration and standard addition methods with good recoveries between 97.1% and 106.2% having relative standard deviation less than 10%.

Etude de la Production de Paires de Leptons dans les Interactions Proton-Beryllium a 450 GEV

NASA Astrophysics Data System (ADS)

Aubry, Pierre Rene Roger

L'experience HELIOS a fait une etude precise de la production des paires e^+e^-, mu^+mu^-, mu ^+mu^-+nu, et mu^+/- e^+/- dans les interactions p-Be a 450 GeV. Le detecteur comporte un spectrometre a electrons, un spectrometre a muons, et un ensemble de calorimetres qui peuvent mesurer les photons et l'energie manquante emportee par les neutrinos. Les paires de leptons sont observees dans la region cinematique ^1: eqalign {2/m_mu 6 GeV cr E_{e}&>2.8 GeV cr.25&directe d'une source encore mal connue de dileptons. La region de masse 0 < m_ll < m_phi est reproduite par la simulation Monte-Carlo des sources connues: desintegrations hadroniques de mesons, charme, bremsstrahlung. L'experience n'a pas observe de production anormale de dielectrons et de dimuons de basses masses dans la region de rapidite centrale. Le spectre en energie manquante permet d'identifier clairement les desintegrations semileptoniques de particules charmees. Une mesure de la section efficace de production de particules charmees dans les interactions p-Be a 450 GeV a ete faite:sigma_{c|c}= 24+/-8 (statistique) +/-16 (systématique) mu barn/nucléon. L'etude de la distribution en energie manquante des dimuons de masse intermediaire (1.2 GeV

Etude de l'influence de la temperature et de l'humidite sur les proprietes mecaniques en traction des fibres de chanvre et de coco

NASA Astrophysics Data System (ADS)

Ho Thi, Thu Nga

L'objectif de cette etude fut d'etablir l'effet de l'humidite et de la temperature sur la resistance en traction et le module elastique des fibres de chanvre et de coco. Deux etudes ont ete realisees afin d'atteindre cet objectif. La premiere vise l'absorption de l'humidite dans ces fibres en exposition dans l'air (de 0%RH a 80%RH) ainsi que l'absorption de l'eau dans ces fibres immergees dans l'eau aux differentes temperatures. La deuxieme consiste a mesurer la resistance en traction et le module elastique de ces fibres sous differentes conditions d'humidite et de temperature. En basant sur les resultats experimentaux obtenus, les methodes semi empiriques et de reseaux de neurones ont ete utilisees pour but de predire les proprietes en traction (resistance et module d'elasticite) des fibres de chanvre et de coco sous l'influence de l'humidite et de la temperature.

Investigations by Protein Film Electrochemistry of Alternative Reactions of Nickel-Containing Carbon Monoxide Dehydrogenase.

PubMed

Wang, Vincent C-C; Islam, Shams T A; Can, Mehmet; Ragsdale, Stephen W; Armstrong, Fraser A

2015-10-29

Protein film electrochemistry has been used to investigate reactions of highly active nickel-containing carbon monoxide dehydrogenases (CODHs). When attached to a pyrolytic graphite electrode, these enzymes behave as reversible electrocatalysts, displaying CO2 reduction or CO oxidation at minimal overpotential. The O2 sensitivity of CODH is suppressed by adding cyanide, a reversible inhibitor of CO oxidation, or by raising the electrode potential. Reduction of N2O, isoelectronic with CO2, is catalyzed by CODH, but the reaction is sluggish, despite a large overpotential, and results in inactivation. Production of H2 and formate under highly reducing conditions is consistent with calculations predicting that a nickel-hydrido species might be formed, but the very low rates suggest that such a species is not on the main catalytic pathway.

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. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2012-03-01

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

Reconstruction de la surface de Fermi dans l'etat normal d'un supraconducteur a haute Tc: Une etude du transport electrique en champ magnetique intense

NASA Astrophysics Data System (ADS)

Le Boeuf, David

Des mesures de resistance longitudinale et de resistance de Hall en champ magnetique intense transverse (perpendiculaire aux plans CuO2) ont ete effectuees au sein de monocristaux de YBa2Cu3Oy (YBCO) demacles, ordonnes et de grande purete, afin d'etudier l'etat fondamental des supraconducteurs a haute Tc dans le regime sous-dope. Cette etude a ete realisee en fonction du dopage et de l'orientation du courant d'excitation J par rapport a l'axe orthorhombique b de la structure cristalline. Les mesures en champ magnetique intense revelent par suppression de la supraconductivite des oscillations magnetiques des resistances longitudinale et de Hall dans YBa2Cu 3O6.51 et YBa2Cu4O8. La conformite du comportement de ces oscillations quantiques au formalisme de Lifshitz-Kosevich, apporte la preuve de l'existence d'une surface de Fermi fermee a caractere quasi-2D, abritant des quasiparticules coherentes respectant la statistique de Fermi-Dirac, dans la phase pseudogap d'YBCO. La faible frequence des oscillations quantiques, combinee avec l'etude de la partie monotone de la resistance de Hall en fonction de la temperature indique que la surface de Fermi d'YBCO sous-dope comprend une petite poche de Fermi occupee par des porteurs de charge negative. Cette particularite de la surface de Fermi dans le regime sous-dope incompatible avec les calculs de structure de bande est en fort contraste avec la structure electronique presente dans le regime surdope. Cette observation implique ainsi l'existence d'un point critique quantique dans le diagramme de phase d'YBCO, au voisinage duquel la surface de Fermi doit subir une reconstruction induite par l'etablissement d'une brisure de la symetrie de translation du reseau cristallin sous-jacent. Enfin, l'etude en fonction du dopage de la resistance de Hall et de la resistance longitudinale en champ magnetique intense suggere qu'un ordre du type onde de densite (DW) est responsable de la reconstruction de la surface de Fermi. L'analogie de

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

PubMed Central

Yuan, Wenjing; Zhou, Yu; Li, Yingru; Li, Chun; Peng, Hailin; Zhang, Jin; Liu, Zhongfan; Dai, Liming; Shi, Gaoquan

2013-01-01

Graphene has a unique atom-thick two-dimensional structure and excellent properties, making it attractive for a variety of electrochemical applications, including electrosynthesis, electrochemical sensors or electrocatalysis, and energy conversion and storage. However, the electrochemistry of single-layer graphene has not yet been well understood, possibly due to the technical difficulties in handling individual graphene sheet. Here, we report the electrochemical behavior at single-layer graphene-based electrodes, comparing the basal plane of graphene to its edge. The graphene edge showed 4 orders of magnitude higher specific capacitance, much faster electron transfer rate and stronger electrocatalytic activity than those of graphene basal plane. A convergent diffusion effect was observed at the sub-nanometer thick graphene edge-electrode to accelerate the electrochemical reactions. Coupling with the high conductivity of a high-quality graphene basal plane, graphene edge is an ideal electrode for electrocatalysis and for the storage of capacitive charges. PMID:23896697

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

DTIC Science & Technology

1993-04-01

PROCEEDINGS 514 OELECTE f Theoretical and A U Experimental Methods in A Hypersonic Flows (Les Methodes Th6oriques et Experimentales pour 1’Etude des...nitrogen ent for both equilibrium and non -equilibrium chemistry between the two groups . Both groups state that the boundary makes this mode even more...flowfield on control is also m?,ndatory unstable due to the necessary oblate shape of Hermes. when the experimental rebuilding is clearly poor and

Determination of psychostimulants and their metabolites by electrochemistry linked on-line to flowing atmospheric pressure afterglow mass spectrometry.

PubMed

Smoluch, Marek; Mielczarek, Przemyslaw; Reszke, Edward; Hieftje, Gary M; Silberring, Jerzy

2014-09-07

The flowing atmospheric pressure afterglow (FAPA) ion source operates in the ambient atmosphere and has been proven to be a promising tool for direct and rapid determination of numerous compounds. Here we linked a FAPA-MS system to an electrochemical flow cell for the identification of drug metabolites generated electrochemically in order to study simulated metabolic pathways. Psychostimulants and their metabolites produced by electrochemistry (EC) were detected on-line by FAPA-MS. The FAPA source has never been used before for an on-line connection with liquid flow, neither for identification of products generated in an electrochemical flow cell. The system was optimized to achieve the highest ionization efficiency by adjusting several parameters, including distances and angles between the ion source and the outlet of the EC system, the high voltage for plasma generation, flow-rates, and EC parameters. Simulated metabolites from tested compounds [methamphetamine (MAF), para-methoxy-N-methylamphetamine (PMMA), dextromethorphan (DXM), and benzydamine (BAM)] were formed in the EC cell at various pH levels. In all cases the main products were oxidized substrates and compounds after N-demethylation. Generation of such products and their thorough on-line identification confirm that the cytochrome P450 - driven metabolism of pharmaceuticals can be efficiently simulated in an electrochemical cell; this approach may serve as a step towards predictive pharmacology using a fast and robust design.

Investigation on direct electrochemical and electrocatalytic behavior of hemoglobin on palladium-graphene modified electrode.

PubMed

Chen, Wei; Niu, Xueliang; Li, Xiaoyan; Li, Xiaobao; Li, Guangjiu; He, Bolin; Li, Qiutong; Sun, Wei

2017-11-01

Palladium-graphene (Pd-GR) nanocomposite was acted as modifier for construction of the modified electrode with direct electrochemistry of hemoglobin (Hb) realized. By using Nafion as the immobilization film, Hb was fixed tightly on Pd-GR nanocomposite modified carbon ionic liquid electrode. Electrochemical behaviors of Hb modified electrode were checked by cyclic voltammetry and a pair of redox peaks originated from direct electron transfer of Hb was appeared. The Hb modified electrode had excellent electrocatalytic activity to the reduction of trichloroacetic acid and sodium nitrite in the concentration range from 0.6 to 13.0mmol·L -1 and from 0.04 to 0.5 mmol·L -1 . Therefore Pd-GR nanocomposite was proven to be a good candidate for the fabrication of third-generation electrochemical biosensor. Copyright © 2017 Elsevier B.V. All rights reserved.

Addressable Direct-Write Nanoscale Filament Formation and Dissolution by Nanoparticle-Mediated Bipolar Electrochemistry.

PubMed

Crouch, Garrison M; Han, Donghoon; Fullerton-Shirey, Susan K; Go, David B; Bohn, Paul W

2017-05-23

Nanoscale conductive filaments, usually associated with resistive memory or memristor technology, may also be used for chemical sensing and nanophotonic applications; however, realistic implementation of the technology requires precise knowledge of the conditions that control the formation and dissolution of filaments. Here we describe and characterize an addressable direct-write nanoelectrochemical approach to achieve repeatable formation/dissolution of Ag filaments across a ∼100 nm poly(ethylene oxide) (PEO) film containing either Ag + alone or Ag + together with 50 nm Ag-nanoparticles acting as bipolar electrodes. Using a conductive AFM tip, formation occurs when the PEO film is subjected to a forward bias, and dissolution occurs under reverse bias. Formation-dissolution kinetics were studied for three film compositions: Ag|PEO-Ag + , Ag|poly(ethylene glycol) monolayer-PEO-Ag + , and Ag|poly(ethylene glycol) monolayer-PEO-Ag + /Ag-nanoparticle. Statistical analysis shows that the distribution of formation times exhibits Gaussian behavior, and the fastest average initial formation time occurs for the Ag|PEO-Ag + system. In contrast, formation in the presence of Ag nanoparticles likely proceeds by a noncontact bipolar electrochemical mechanism, exhibiting the slowest initial filament formation. Dissolution times are log-normal for all three systems, and repeated reformation of filaments from previously formed structures is characterized by rapid regrowth. The direct-write bipolar electrochemical deposition/dissolution strategy developed here presents an approach to reconfigurable, noncontact in situ wiring of nanoparticle arrays-thereby enabling applications where actively controlled connectivity of nanoparticle arrays is used to manipulate nanoelectronic and nanophotonic behavior. The system further allows for facile manipulation of experimental conditions while simultaneously characterizing surface conditions and filament formation/dissolution kinetics.

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

PubMed

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

2018-05-09

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

99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

PubMed

McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

2012-08-20

The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

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.

Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

2015-10-01

Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

Simulating Electrochemistry of Hydrothermal Vents on Enceladus and Other Ocean Worlds

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

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.

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

PubMed

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

2010-10-01

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

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.

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

PubMed

Miao, Fengjuan; Tao, Bairui; Chu, Paul K

2012-04-28

A new silicon-based anode suitable for direct ethanol fuel cells (DEFCs) is described. Pd-Ni nanoparticles are coated on Si nanowires (SiNWs) by electroless co-plating to form the catalytic materials. The electrocatalytic properties of the SiNWs and ethanol oxidation on the Pd-Ni catalyst (Pd-Ni/SiNWs) are investigated electrochemically. The effects of temperature and working potential limit in the anodic direction on ethanol oxidation are studied by cyclic voltammetry. The Pd-Ni/SiNWs electrode exhibits higher electrocatalytic activity and better long-term stability in an alkaline solution. It also yields a larger current density and negative onset potential thus boding well for its application to fuel cells. This journal is © The Royal Society of Chemistry 2012

STM, SECPM, AFM and Electrochemistry on Single Crystalline Surfaces

PubMed Central

Wolfschmidt, Holger; Baier, Claudia; Gsell, Stefan; Fischer, Martin; Schreck, Matthias; Stimming, Ulrich

2010-01-01

Scanning probe microscopy (SPM) techniques have had a great impact on research fields of surface science and nanotechnology during the last decades. They are used to investigate surfaces with scanning ranges between several 100 μm down to atomic resolution. Depending on experimental conditions, and the interaction forces between probe and sample, different SPM techniques allow mapping of different surface properties. In this work, scanning tunneling microscopy (STM) in air and under electrochemical conditions (EC-STM), atomic force microscopy (AFM) in air and scanning electrochemical potential microscopy (SECPM) under electrochemical conditions, were used to study different single crystalline surfaces in electrochemistry. Especially SECPM offers potentially new insights into the solid-liquid interface by providing the possibility to image the potential distribution of the surface, with a resolution that is comparable to STM. In electrocatalysis, nanostructured catalysts supported on different electrode materials often show behavior different from their bulk electrodes. This was experimentally and theoretically shown for several combinations and recently on Pt on Au(111) towards fuel cell relevant reactions. For these investigations single crystals often provide accurate and well defined reference and support systems. We will show heteroepitaxially grown Ru, Ir and Rh single crystalline surface films and bulk Au single crystals with different orientations under electrochemical conditions. Image studies from all three different SPM methods will be presented and compared to electrochemical data obtained by cyclic voltammetry in acidic media. The quality of the single crystalline supports will be verified by the SPM images and the cyclic voltammograms. Furthermore, an outlook will be presented on how such supports can be used in electrocatalytic studies. PMID:28883327

Surface Electrochemistry of Metals

DTIC Science & Technology

1993-04-30

maxima along the 12 directions of open channels .vhich are also the interatomic directions). Elastic scattering angular distributions always contain... scatterer geometric relationships for such samples. Distributions from ordered atomic bilayers reveal that the Auger signal from the underlayer is attenuated...are developing a theoretical model and computational code which include both elastic scattering and inhomogeneous inelastic scattering . We seek

Epitaxial Fe(1-x)Gax/GaAs structures via electrochemistry for spintronics applications

NASA Astrophysics Data System (ADS)

Reddy, K. Sai Madhukar; Maqableh, Mazin M.; Stadler, Bethanie J. H.

2012-04-01

In this study, thin films of Fe83Ga17 (a giant magnetostrictive alloy) were grown on single-crystalline n-GaAs (001) and polycrystalline brass substrates via electrochemical synthesis from ferrous and gallium sulfate electrolytes. Extensive structural characterization using microdiffraction, high-resolution ω - 2θ, and rocking-curve analysis revealed that the films grown on GaAs(001) are highly textured with ⟨001⟩ orientation along the substrate normal, and the texture improved further upon annealing at 300 °C for 2 h in N2 environment. On the contrary, films grown on brass substrates exhibited ⟨011⟩ preferred orientation. Rocking-curve analysis done on Fe83Ga17/GaAs structures further confirmed that the ⟨001⟩ texture in the Fe83Ga17 thin film is a result of epitaxial nucleation and growth. The non-linear current-voltage plot obtained for the Fe-Ga/GaAs Schottky contacts was characteristic of tunneling injection, and showed improved behavior with annealing. Thus, this study demonstrates the feasibility of fabricating spintronic devices that incorporate highly magnetostrictive Fe(1-x)Gax thin films grown epitaxially via electrochemistry.

Introduction A l'Etude de la Médecine Expérimentale--surgical revolution part II.

PubMed

Toledo-Pereyra, Luis H

2009-01-01

The book that Claude Bernard (1813-1878) published in 1865, the Introduction à l'Etude de la Médecine Expérimentale, fostered a revolution that we believe influenced the practice of surgery when the discipline became a scientific enterprise. In Part I, we set the stage by presenting the life and accomplishments of Bernard, by reviewing his science, and introducing his experimental medicine work. In this issue in Part II, we further analyze his book and determine the "why" of a genuine surgical revolution. What were the factors that generated this revolution, and how a new generation of surgeons learned to become better researchers, and thus better surgeons, were the main objectives of this work. Science, research, and surgery became highly intertwined and the surgeon pursued these fields of knowledge more effectively.

Electrochemistry of Prebiotic Early Earth Hydrothermal Chimney Systems

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Progress in Aluminum Electrolysis Control and Future Direction for Smart Aluminum Electrolysis Plant

NASA Astrophysics Data System (ADS)

Zhang, Hongliang; Li, Tianshuang; Li, Jie; Yang, Shuai; Zou, Zhong

2017-02-01

The industrial aluminum reduction cell is an electrochemistry reactor that operates under high temperatures and highly corrosive conditions. However, these conditions have restricted the measurement of key control parameters, making the control of aluminum reduction cells a difficult problem in the industry. Because aluminum electrolysis control systems have a significant economic influence, substantial research has been conducted on control algorithms, control systems and information systems for aluminum reduction cells. This article first summarizes the development of control systems and then focuses on the progress made since 2000, including alumina concentration control, temperature control and electrolyte molecular ratio control, fault diagnosis, cell condition prediction and control system expansion. Based on these studies, the concept of a smart aluminum electrolysis plant is proposed. The frame construction, key problems and current progress are introduced. Finally, several future directions are discussed.

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

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.

Multi-layer membrane model for mass transport in a direct ethanol fuel cell using an alkaline anion exchange membrane

NASA Astrophysics Data System (ADS)

Bahrami, Hafez; Faghri, Amir

2012-11-01

A one-dimensional, isothermal, single-phase model is presented to investigate the mass transport in a direct ethanol fuel cell incorporating an alkaline anion exchange membrane. The electrochemistry is analytically solved and the closed-form solution is provided for two limiting cases assuming Tafel expressions for both oxygen reduction and ethanol oxidation. A multi-layer membrane model is proposed to properly account for the diffusive and electroosmotic transport of ethanol through the membrane. The fundamental differences in fuel crossover for positive and negative electroosmotic drag coefficients are discussed. It is found that ethanol crossover is significantly reduced upon using an alkaline anion exchange membrane instead of a proton exchange membrane, especially at current densities higher than 500 A m

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

PubMed

Faber, Helene; Melles, Daniel; Brauckmann, Christine; Wehe, Christoph Alexander; Wentker, Kristina; Karst, Uwe

2012-04-01

Diclofenac is a frequently prescribed drug for rheumatic diseases and muscle pain. In rare cases, it may be associated with a severe hepatotoxicity. In literature, it is discussed whether this toxicity is related to the oxidative phase I metabolism, resulting in electrophilic quinone imines, which can subsequently react with nucleophiles present in the liver in form of glutathione or proteins. In this work, electrochemistry coupled to mass spectrometry is used as a tool for the simulation of the oxidative pathway of diclofenac. Using this purely instrumental approach, diclofenac was oxidized in a thin layer cell equipped with a boron doped diamond working electrode. Sum formulae of generated oxidation products were calculated based on accurate mass measurements with deviations below 2 ppm. Quinone imines from diclofenac were detected using this approach. It could be shown for the first time that these quinone imines do not react with glutathione exclusively but also with larger molecules such as the model protein β-lactoglobulin A. A tryptic digest of the generated drug-protein adduct confirms that the protein is modified at the only free thiol-containing peptide. This simple and purely instrumental set-up offers the possibility of generating reactive metabolites of diclofenac and to assess their reactivity rapidly and easily.

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.

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 �

Interconnection of Key Microbial Functional Genes for Enhanced Benzo[a]pyrene Biodegradation in Sediments by Microbial Electrochemistry.

PubMed

Yan, Zaisheng; He, Yuhong; Cai, Haiyuan; Van Nostrand, Joy D; He, Zhili; Zhou, Jizhong; Krumholz, Lee R; Jiang, He-Long

2017-08-01

Sediment microbial fuel cells (SMFCs) can stimulate the degradation of polycyclic aromatic hydrocarbons in sediments, but the mechanism of this process is poorly understood at the microbial functional gene level. Here, the use of SMFC resulted in 92% benzo[a]pyrene (BaP) removal over 970 days relative to 54% in the controls. Sediment functions, microbial community structure, and network interactions were dramatically altered by the SMFC employment. Functional gene analysis showed that c-type cytochrome genes for electron transfer, aromatic degradation genes, and extracellular ligninolytic enzymes involved in lignin degradation were significantly enriched in bulk sediments during SMFC operation. Correspondingly, chemical analysis of the system showed that these genetic changes resulted in increases in the levels of easily oxidizable organic carbon and humic acids which may have resulted in increased BaP bioavailability and increased degradation rates. Tracking microbial functional genes and corresponding organic matter responses should aid mechanistic understanding of BaP enhanced biodegradation by microbial electrochemistry and development of sustainable bioremediation strategies.

Etude de l'affaiblissement du comportement mecanique du pergelisol du au rechauffement climatique

NASA Astrophysics Data System (ADS)

Buteau, Sylvie

Le rechauffement climatique predit pour les prochaines decennies, aura des impacts majeurs sur le pergelisol qui sont tres peu documentes pour l'instant. La presente etude a pour but d'evaluer ces impacts sur les proprietes mecaniques du pergelisol et sa stabilite a long terme. Une nouvelle technique d'essai de penetration au cone a taux de deformation controle, a ete developpee pour caracteriser en place le pergelisol. Ces essais geotechniques et la mesure de differentes proprietes physiques ont ete effectues sur une butte de pergelisol au cours du printemps 2000. Le developpement et l'utilisation d'un modele geothermique 1D tenant compte de la thermodependance du comportement mecanique ont permis d'evaluer que les etendues de pergelisol chaud deviendraient instables a la suite d'un rechauffement de l'ordre de 5°C sur cent ans. En effet, la resistance mecanique du pergelisol diminuera alors rapidement jusqu'a 11,6 MPa, ce qui correspond a une perte relative de 98% de la resistance par rapport a un scenario sans rechauffement.

Electrochemistry at a Metal Nanoparticle on a Tunneling Film: A Steady-State Model of Current Densities at a Tunneling Ultramicroelectrode.

PubMed

Hill, Caleb M; Kim, Jiyeon; Bard, Allen J

2015-09-09

Here, a new methodology is proposed for treating electrochemical current densities in metal-insulator-metal nanoparticle (M-I-MNP) systems. The described model provides broad, practical insights about MNP-mediated electron transfer to redox species in solution, where electron transfer from the underlying electrode to a MNP via tunneling and heterogeneous electron transfer from the MNP to redox species in solution are treated as sequential steps. Tunneling is treated through an adaptation of the Simmons model of tunneling in metal-insulator-metal structures, and explicit equations are provided for tunneling currents, which demonstrate the effect of various experimental parameters, such as insulator thickness and MNP size. Overall, a general approach is demonstrated for determining experimental conditions where tunneling will have a measurable impact on the electrochemistry of M-I-MNP systems.

The abject gaze and the homosexual body: Flandrin's Figure d'Etude.

PubMed

Camille, M

1994-01-01

This article charts the history of the reception, reproduction and appropriation of a single image that has recently become a kind of "gay icon"--the Figure d'Etude in the Louvre, painted by Hippolyte Flandrin in 1835. Initially no more than a neo-classical academic exercise, the formal emptiness of this picture meant that it could be re-invested and reinscribed with new meanings and new titles at every turn. Emblematic of the anxious visibility/invisibility of the newly discovered homosexual body during a period when the gaze still had to be kept a dark secret, Flandrin's image only "came out" in its later photographic reworkings by Frederick Holland Day and Baron von Gloeden. After being reproduced for a specifically homosexual audience early this century, the popular Romantic pose of the young man curled-up in profile became a standard one, reappearing recently in the photographs of Robert Mapplethorpe. The inactive, abject and inward-turned isolation of the figure with its narcissistic self-absorption makes it, in my view, a profoundly negative stereotype of the gay gaze and the homosexual body. Flandrin's figure nonetheless appears today on gay merchandise world-wide as a sign of our separate and secluded subject positions and our community's unwillingness to radically alter older imposed and inherited classical stereotypes.

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

Observation of nanometer-sized electro-active defects in insulating layers by fluorescence microscopy and electrochemistry.

PubMed

Renault, Christophe; Marchuk, Kyle; Ahn, Hyun S; Titus, Eric J; Kim, Jiyeon; Willets, Katherine A; Bard, Allen J

2015-06-02

We report a method to study electro-active defects in passivated electrodes. This method couples fluorescence microscopy and electrochemistry to localize and size electro-active defects. The method was validated by comparison with a scanning probe technique, scanning electrochemical microscopy. We used our method for studying electro-active defects in thin TiO2 layers electrodeposited on 25 μm diameter Pt ultramicroelectrodes (UMEs). The permeability of the TiO2 layer was estimated by measuring the oxidation of ferrocenemethanol at the UME. Blocking of current ranging from 91.4 to 99.8% was achieved. Electro-active defects with an average radius ranging between 9 and 90 nm were observed in these TiO2 blocking layers. The distribution of electro-active defects over the TiO2 layer is highly inhomogeneous and the number of electro-active defect increases for lower degree of current blocking. The interest of the proposed technique is the possibility to quickly (less than 15 min) image samples as large as several hundreds of μm(2) while being able to detect electro-active defects of only a few tens of nm in radius.

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

DOE PAGES

Staszak-Jirkovsky, Jakub; Subbaraman, Ram; Strmcnik, Dusan; ...

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 favorablemore » 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.« less

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".

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

PubMed

Barbosa, Nuno Almeida; Grzeszczuk, Maria; Wieczorek, Robert

2015-01-15

First results of the application of the DFT computational approach to the reversible electrochemistry of polyaniline are presented. A tetrameric chain was used as the simplest model of the polyaniline polymer species. The system under theoretical investigation involved six tetramer species, two electrons, and two protons, taking part in 14 elementary reactions. Moreover, the tetramer species were interacting with two trihalogenoacetic acid molecules. Trifluoroacetic, trichloroacetic, and tribromoacetic acids were found to impact the redox transformation of polyaniline as shown by cyclic voltammetry. The theoretical approach was considered as a powerful tool for investigating the main factors of importance for the experimental behavior. The DFT method provided molecular structures, interaction energies, and equilibrium energies of all of the tetramer-acid complexes. Differences between the energies of the isolated tetramer species and their complexes with acids are discussed in terms of the elementary reactions, that is, ionization potentials and electron affinities, equilibrium constants, electrode potentials, and reorganization energies. The DFT results indicate a high impact of the acid on the reorganization energy of a particular elementary electron-transfer reaction. The ECEC oxidation path was predicted by the calculations. The model of the reacting system must be extended to octamer species and/or dimeric oligomer species to better approximate the real polymer situation.

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

PubMed

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

2018-02-13

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

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

PubMed

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

2015-05-06

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

Direct Electrochemistry of Glucose Oxidase on Novel Free-Standing Nitrogen-Doped Carbon Nanospheres@Carbon Nanofibers Composite Film

PubMed Central

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

2015-01-01

We have proposed a novel free-standing nitrogen-doped carbon nanospheres@carbon nanofibers (NCNSs@CNFs) composite film with high processability for the investigation of the direct electron transfer (DET) of glucose oxidase (GOx) and the DET-based glucose biosensing. The composites were simply prepared by controlled thermal treatment of electrospun polypyrrole nanospheres doped polyacrylonitrile nanofibers (PPyNSs@PAN NFs). Without any pretreatment, the as-prepared material can directly serve as a platform for GOx immobilization. The cyclic voltammetry of immobilized GOx showed a pair of well-defined redox peaks in O2-free solution, indicating the DET of GOx. With the addition of glucose, the anodic peak current increased, while the cathodic peak current decreased, which demonstrated the DET-based bioelectrocatalysis. The detection of glucose based on the DET of GOx was achieved, which displayed high sensitivity, stability and selectivity, with a low detection limit of 2 μM and wide linear range of 12–1000 μM. These results demonstrate that the as-obtained NCNSs@CNFs can serve as an ideal platform for the construction of the third-generation glucose biosensor. PMID:25943704

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

PubMed

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

2013-09-11

Two new 2,2'-bipyridine (bpy) derivatives containing ancillary BODIPY chromophores attached at the 5- and 5'-positions (BB3) or 6- and 6'-positions (BB4) were prepared and characterized. In this work, the basic photophysics, electrochemistry, and electrogenerated chemiluminescence (ECL) of BB3 and BB4 are compared with those previously reported for a related bpy-BODIPY derivative (BB2) (J. Phys. Chem. C 2011, 115, 17993-18001). Cyclic voltammetry revealed that BB3 and BB4 display reversible 2e(-) oxidation and reduction waves, which consist of two closely spaced (50-70 mV) 1e(-) events. This redox behavior is consistent with the frontier molecular orbitals calculated for BB3 and BB4 and indicates that the 2,2'-bipyridine spacer of each bpy-BODIPY homologue does not facilitate efficient electronic communication between the tethered indacene units. In the presence of a coreactant such as tri-n-propylamine (TPA) or benzoyl peroxide (BPO), BB3 and BB4 exhibit strong ECL and produce spectra that are very similar to their corresponding photoluminescence profiles. The ECL signal obtained under annihilation conditions, however, is significantly different and is characterized by two distinct bands. One of these bands is centered at ∼570 nm and is attributed to emission via an S- or T-route. The second band occurs at longer wavelengths and is centered around ∼740 nm. The shape and concentration dependence of this long-wavelength ECL signal is not indicative of emission from an excimer or aggregate, but rather it suggests that a new emissive species is formed from the bpy-BODIPY luminophores during the annihilation process.

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

PubMed Central

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

2014-01-01

Two new 2,2’-bipyridine (bpy) derivatives containing ancillary BODIPY chromophores attached at the 5- and 5’-positions (BB3) or 6- and 6’-positions (BB4) were prepared and characterized. In this work, the basic photophysics, electrochemistry and electrogenerated chemiluminescence (ECL) of BB3 and BB4 are compared with those previously reported for a related bpy-BODIPY derivative (BB2) (J. Phys. Chem. C 2011, 115, 17993–18001). Cyclic voltammetry revealed that BB3 and BB4 display reversible 2e− oxidation and reduction waves, which consist of two closely spaced (50 – 70 mV) 1e− events. This redox behavior is consistent with the frontier molecular orbitals calculated for BB3 and BB4 and indicates that the 2,2’-bipyridine spacer of each bpy- BODIPY homologue does not facilitate efficient electronic communication between the tethered indacene units. In the presence of a coreactant such as tri-n-propylamine (TPA) or benzoyl peroxide (BPO), BB3 and BB4 exhibit strong ECL and produce spectra that are very similar to their corresponding photoluminescence profiles. The ECL signal obtained under annihilation conditions, however, is significantly different and is characterized by two distinct bands. One of these bands is centered at ~570 nm and is attributed to emission via an S- or T-route. The second band, occurs at longer wavelengths and is centered around ~740 nm. The shape and concentration dependence of this long-wavelength ECL signal is not indicative of emission from an excimer or aggregate, but rather is suggests that a new emissive species is formed from the bpy-BODIPY luminophores during the annihilation process. PMID:23980850

Synthesis and electrochemistry of heterobimetallic ruthenium/platinum and molybdenum/platinum complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orth, S.D.; Terry, M.R.; Abboud, K.A.

1996-02-14

As starting materials for heterobimetallic complexes, [RuCp(PPh{sub 3})CO(PPh{sub 2}H)]PF{sub 6} and [RuCp(PPh{sub 3})CO({eta}-dppm)]-PF{sub 6} were prepared from RuCp(PPh{sub 3})(CO)Cl. In the course of preparing [RuCp({eta}{sup 2}-dppm)({eta}-dppm)]Cl from RuCp(Ph{sub 3}P)({eta}-dppm)Cl, the monomer RuCpCl({eta}-dppm){sub 2} was isolated. The uncommon coordination mode of the two monodentatebis(phosphines) was confirmed by X-ray crystallography [a = 11.490(1) {angstrom}, b = 14.869(2) {angstrom}, c = 15.447(2) {angstrom}, {alpha} = 84.63(1){degrees}, {beta} = 70.55(1){degrees}, {gamma} = 72.92(1){degrees}, V = 2378.7(5) {angstrom}{sup 3}, d{sub calc} = 1.355 g cm{sup -3} (298 K), triclinic, P1, Z = 2]. The dppm-bridged bimetallic complexes RuCp(PPh{sub 3})Cl({mu}-dppm)PtCl{sub 2}, RuCpCl({mu}-dppm){sub 2}PtCl{sub 2}, and [RuCp(PPh{submore » 3})CO({mu}-dppm)PtCl{sub 2}]PF{sub 6} each exhibit electrochemistry consistent with varying degrees of metal-metal interaction. The cationic heterobimetallic complexes [Mo(CO){sub 3}({mu}-dppm){sub 2}Pt(H)]PF{sub 6} and [MoCp-(CO){sub 2}-({mu}-PPh{sub 2})({mu}-H)Pt(PPh{sub 3})(MeCN)]PF{sub 6} were prepared by chloride abstraction from the corresponding neutral bimetallic species and show electrochemical behavior similar to the analogous Ru/Pt complexes.« less

Direct electrochemistry and electrocatalysis of hemoglobin in graphene oxide and ionic liquid composite film.

PubMed

Sun, Wei; Gong, Shixing; Shi, Fan; Cao, Lili; Ling, Luyang; Zheng, Weizhe; Wang, Wencheng

2014-07-01

In this paper a novel sensing platform based on graphene oxide (GO), ionic liquid (IL) 1-ethyl-3-methylimidazolium tetrafluoroborate and Nafion for the immobilization of hemoglobin (Hb) was adopted with a carbon ionic liquid electrode (CILE) as the substrate electrode, which was denoted as Nafion/Hb-GO-IL/CILE. Spectroscopic results suggested that Hb molecules were not denatured in the composite. A pair of well-defined redox peaks appeared on the cyclic voltammogram, which was attributed to the realization of direct electron transfer of Hb on the electrode. Electrochemical behaviors of Hb entrapped in the film were carefully investigated by cyclic voltammetry with the electrochemical parameters calculated. Based on the catalytic ability of the immobilized Hb, Nafion/Hb-GO-IL/CILE exhibited excellent electrocatalytic behavior towards the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.01 to 40.0mM with the detection limit as 3.12 μM (3σ), H2O2 in the concentration range from 0.08 to 635.0 μM with the detection limit as 0.0137 μM (3σ) and NaNO2 in the concentration range from 0.5 to 800.0 μM with the detection limit as 0.0104 μM (3σ). So the proposed bioelectrode could be served as a new third-generation electrochemical sensor without mediator. Copyright © 2014 Elsevier B.V. All rights reserved.

L'etude de l'InP et du GaP suite a l'implantation ionique de Mn et a un recuit thermique

NASA Astrophysics Data System (ADS)

Bucsa, Ioan Gigel

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

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

PubMed Central

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

2015-01-01

This study presents the development of ultra-performance liquid chromatography/mass spectrometry (UPLC/MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of disulfide bond-containing proteins/peptides. In our approach, a protein/peptide mixture sample undergoes fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and MS/MS analyses. The electrochemical cell is coupled to MS using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, disulfide bond-containing peptides can be differentiated from those without disulfide bonds as the former are electroactive and reducible. Tandem MS analysis of the disulfide-reduced peptide ions provides increased sequence and disulfide linkage pattern information. In a reactive DESI-MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which would be useful in top-down protein structure analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1~2 orders of magnitude by using UPLC for the LC/EC/MS platform, in comparison to the previously used high performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis. PMID:26307715

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

PubMed

Tan, Shu Min; Pumera, Martin

2017-12-06

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

Ultrasensitive signal-on DNA biosensor based on nicking endonuclease assisted electrochemistry signal amplification.

PubMed

Liu, Zhongyuan; Zhang, Wei; Zhu, Shuyun; Zhang, Ling; Hu, Lianzhe; Parveen, Saima; Xu, Guobao

2011-11-15

Combining the advantages of signal-on strategy and nicking endonuclease assisted electrochemistry signal amplification (NEAESA), a new sensitive and signal-on electrochemical DNA biosensor for the sequence specific DNA detection based on NEAESA has been developed for the first time. A Hairpin-shape probe (HP), containing the target DNA recognition sequence, is thiol-modified at 5' end and immobilized on gold electrode via Au-S bonding. Subsequently, the HP modified electrode is hybridized with target DNA to form a duplex. Then the nicking endonuclease is added and nicks the HP strand in the duplex. After nicking, 3'-ferrocene (Fc)-labeled part complementary probe (Fc-PCP) is introduced on the electrode surface by hybridizing with the thiol-modified HP fragment, which results in the generation of electrochemical signal. Hence, the DNA biosensor is constructed successfully. The present DNA biosensor shows a wide linear range of 5.0×10(-13)-5.0×10(-8)M for detecting target DNA, with a low detection limit of 0.167pM. The proposed strategy does not require any amplifying labels (enzymes, DNAzymes, nanoparticles, etc.) for biorecognition events, which avoids false-positive results to occur frequently. Moreover, the strategy has the benefits of simple preparation, convenient operation, good selectivity, and high sensitivity. With the advantages mentioned above, this simple and sensitive strategy has the potential to be integrated in portable, low cost and simplified devices for diagnostic applications. Copyright © 2011 Elsevier B.V. All rights reserved.

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

Dispersion of nanocrystalline Fe 3O 4 within composite electrodes: Insights on battery-related electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

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, Fe 3O 4, 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 Fe 3O 4 dispersion. Electrochemical testing showed that Fe 3O 4 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 themore » dispersed Fe 3O 4 composites relative to the aggregated Fe 3O 4 composites. X-ray absorption spectroscopy measurements of electrodes post cycling indicated that the dispersed Fe 3O 4 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 Fe 3O 4 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

Dispersion of Nanocrystalline Fe 3 O 4 within Composite Electrodes: Insights on Battery-Related Electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei

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, Fe 3O 4, 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 Fe 3O 4 dispersion. Electrochemical testing showed that Fe 3O 4 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 themore » dispersed Fe 3O 4 composites relative to the aggregated Fe 3O 4 composites. X-ray absorption spectroscopy measurements of electrodes post cycling indicated that the dispersed Fe 3O 4 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 Fe 3O 4 compared to the aggregated materials. This study provides insight into the specific effects of aggregation on electrochemistry through a multiscale view of mechanisms for magnetite composite electrodes.« less

Surface chemistry of bulk nanocrystalline pure iron and electrochemistry study in gas-flow physiological saline.

PubMed

Nie, F L; Zheng, Y F

2012-07-01

Conventional microcrystalline pure iron (MC-Fe) becomes a new candidate as biodegradable metals, which has the insufficient physical feature and inferior biodegradation behavior. Novel bulk nanocrystalline pure iron (NC-Fe) was fabricated via equal channel angular pressing technique in the present work to overcome these problems. The contact angle test with water and glycerol droplets shows a smaller angle (though >90°) of NC-Fe than that of MC-Fe, which implies a lower surface energy of NC-Fe. The surface roughness of NC-Fe increased greatly than that of MC-Fe. A further comparative study of corrosion and electrochemistry performance between NC-Fe and its original MC-Fe was investigated in physiological saline with different dissolved oxygen concentration, aiming to in vitro simulate the corrosion process of coronary stent occurred in physiological environment. The electrochemical impedance spectra analysis and anodic polarization measurements indicated that the NC-Fe exhibited higher corrosion resistance than that of the MC-Fe; meanwhile obvious enhanced corrosion resistance with the decrement of dissolved oxygen concentration was observed. Related equivalent circuit model and surface reconstruction process were further discussed, and the degradation mechanism of the MC-Fe and NC-Fe were finally established. Copyright © 2012 Wiley Periodicals, Inc.

Electrochemistry coupled online to liquid chromatography-mass spectrometry for fast simulation of biotransformation reactions of the insecticide chlorpyrifos.

PubMed

Mekonnen, Tessema F; Panne, Ulrich; Koch, Matthias

2017-05-01

An automated method is presented for fast simulation of (bio)transformation products (TPs) of the organophosphate insecticide chlorpyrifos (CPF) based on electrochemistry coupled online to liquid chromatography-mass spectrometry (EC-LC-MS). Oxidative TPs were produced by a boron doped diamond (BDD) electrode, separated by reversed phase HPLC and online detected by electrospray ionization-mass spectrometry (ESI-MS). Furthermore, EC oxidative TPs were investigated by HPLC-tandem mass spectrometry (LC-MS/MS) and FT-ICR high resolution mass spectrometry (HRMS) and compared to in vitro assay metabolites (rat and human liver microsomes). Main phase I metabolites of CPF: chlorpyrifos oxon (CPF oxon), trichloropyridinol (TCP), diethylthiophosphate (DETP), diethylphosphate (DEP), desethyl chlorpyrifos (De-CPF), and desethyl chlorpyrifos oxon (De-CPF oxon), were successfully identified by the developed EC-LC-MS method. The EC-LC-MS method showed similar metabolites compared to the in vitro assay with possibilities of determining reactive species. Our results reveal that online EC-(LC)-MS brings an advantage on time of analysis by eliminating sample preparation steps and matrix complexity compared to conventional in vivo or in vitro methods.

Synthesis, characterization and electrochemistry studies of iron(III) complex with curcumin ligand.

PubMed

Özbolat, Gülüzar; Yegani, Arash Alizadeh; Tuli, Abdullah

2018-05-11

Iron overload is a serious clinical condition for humans and is a key target in drug development. The aim of this study was to investigate the coordination of iron(III) ions with curcumin ligand that may be used in the treatment of iron overload. Iron(III) complex of curcumin was synthesized and structurally characterized in its solid and solution state by FT-IR, UV-Vis, elemental analysis, and magnetic susceptibility. Electrochemical behaviour of the ligand and the complexes were examined using cyclic voltammetry. The cytotoxic activities of the ligand and the iron(III) complex were evaluated by the MTT assay. Curcumin reacted with iron in high concentrations at physiological pH at room temperature. Subsequently, a brown-red complex was formed. Data regarding magnetic susceptibility showed that the complexes with a 1:2 (metal/ligand) mole ratio had octahedral geometry. The complex showed higher anti-oxidant effect towards the cell line ECV304 at IC 50 values of 4.83 compared to curcumin. The complex exhibited very high cytotoxic activity and showed a cytotoxic effect that was much better than that of the ligand. The potentials for redox were calculated as 0.180 V and 0.350 V, respectively. The electrochemistry studies showed that Fe 3+ /Fe 2+ couple redox process occurred at low potentials. This value was within the range of compounds that are expected to show superoxide dismutase activity. This finding indicates that the iron complex is capable of removing free radicals. The observed cytotoxicity could be pursued to obtain a potential drug. Further studies investigating the use of curcumin for this purpose are needed. © 2018 John Wiley & Sons Australia, Ltd.

Etude vibroacoustique d'un systeme coque-plancher-cavite avec application a un fuselage simplifie

NASA Astrophysics Data System (ADS)

Missaoui, Jemai

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

Etude spectroscopique des collisions moleculaires (hydrogene-azote et hydrogene-oxygene) a des energies de quelques MeV

NASA Astrophysics Data System (ADS)

Plante, Jacinthe

1998-09-01

Les resultats presentes ici proviennent d'une etude systematique portant sur les collisions a vitesse constante, entre les projectiles d'hydrogene (H+, H2+ et H3+ a 1 MeV/nucleon) et deux cibles gazeuses (N2 et O2), soumises a differentes pressions. Les collisions sont analysees a l'aide des spectres d'emission (de 400 A a 6650 A) et des graphiques intensite/pression. Les spectres ont revele la presence des raies d'azote atomique, d'azote moleculaire, d'oxygene atomique, d'oxygene moleculaire et d'hydrogene atomique. Les raies d'hydrogene sont observees seulement avec les projectiles H2+ et H3+. Donc les processus responsables de la formation de ces raies sont des mecanismes de fragmentation des projectiles. Pour conclure, il existe une difference notable entre les projectiles et les differentes pressions. Les raies d'azote et d'oxygene augmentent selon la pression et les raies d'hydrogene atomique presentent une relation non lineaire avec la pression.

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

NASA Astrophysics Data System (ADS)

Denoyer, Aurelie

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

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

Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durham, Jessica L.; Huang, Jianping; Zhang, Bingjie

In this paper, silver hollandite (Ag 1.4Mn 8O 16) has been synthesized by an aqueous, low-temperature co-precipitation technique to afford silver hollandite with distinct crystallite sizes (10 and 15 nm, identified as S-Ag 1.4Mn 8O 16 and L-Ag 1.4Mn 8O 16, respectively) and equivalent silver content (x), allowing for the deconvolution of electrochemical effects related to crystallite size and silver content. The as-prepared silver hollandite materials were confirmed to be structurally analogous. Notably, TEM imaging reveals a high degree of bundling of S-Ag 1.4Mn 8O 16 nanorods compared to L-Ag 1.4Mn 8O 16 which facilitates more intimate connection of themore » S-Ag 1.4Mn 8O 16 material with enhanced interparticle contact. The electrochemical behavior and lithium diffusion properties were investigated by galvanostatic cycling, CV, electrochemical impedance, pulsed-discharge experiments, and ex-situ XAS analysis of cycled cathodes. Lithium based electrochemical cells containing S-Ag 1.4Mn 8O 16 delivered a capacity 15X higher than L-Ag 1.4Mn 8O 16 on cycle 1. Ex-situ XAS demonstrated structural change for S-Ag 1.4Mn 8O 16 and formation of Ag 0 on insertion of 3.8 Li + intercalation. However, the samples of L-Ag 1.4Mn 8O 16 were lithiated by a more limited 0.25 molar equivalents, where no significant structural changes were observed. Finally, the findings affirm crystallite size significantly impacts electrochemistry independent of cation occupancy of the α-MnO 2 type structure.« less

Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry

DOE PAGES

Durham, Jessica L.; Huang, Jianping; Zhang, Bingjie; ...

2017-12-16

In this paper, silver hollandite (Ag 1.4Mn 8O 16) has been synthesized by an aqueous, low-temperature co-precipitation technique to afford silver hollandite with distinct crystallite sizes (10 and 15 nm, identified as S-Ag 1.4Mn 8O 16 and L-Ag 1.4Mn 8O 16, respectively) and equivalent silver content (x), allowing for the deconvolution of electrochemical effects related to crystallite size and silver content. The as-prepared silver hollandite materials were confirmed to be structurally analogous. Notably, TEM imaging reveals a high degree of bundling of S-Ag 1.4Mn 8O 16 nanorods compared to L-Ag 1.4Mn 8O 16 which facilitates more intimate connection of themore » S-Ag 1.4Mn 8O 16 material with enhanced interparticle contact. The electrochemical behavior and lithium diffusion properties were investigated by galvanostatic cycling, CV, electrochemical impedance, pulsed-discharge experiments, and ex-situ XAS analysis of cycled cathodes. Lithium based electrochemical cells containing S-Ag 1.4Mn 8O 16 delivered a capacity 15X higher than L-Ag 1.4Mn 8O 16 on cycle 1. Ex-situ XAS demonstrated structural change for S-Ag 1.4Mn 8O 16 and formation of Ag 0 on insertion of 3.8 Li + intercalation. However, the samples of L-Ag 1.4Mn 8O 16 were lithiated by a more limited 0.25 molar equivalents, where no significant structural changes were observed. Finally, the findings affirm crystallite size significantly impacts electrochemistry independent of cation occupancy of the α-MnO 2 type structure.« less

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.

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

Direct electrochemistry of hemoglobin on graphene and titanium dioxide nanorods composite modified electrode and its electrocatalysis.

PubMed

Sun, Wei; Guo, Yaqing; Ju, Xiaomei; Zhang, Yuanyuan; Wang, Xiuzhen; Sun, Zhenfan

2013-04-15

A biocompatible sensing platform based on graphene (GR) and titanium dioxide (TiO₂) nanorods for the immobilization of hemoglobin (Hb) was adopted in this paper. The GR-TiO₂-Hb composite-modified carbon ionic liquid electrode was constructed through a simple casting method with Nafion as the film forming material. UV-Vis and FT-IR spectra confirmed that Hb retained its native structure in the composite film. Direct electron transfer of Hb incorporated into the composite was realized with a pair of quasi-reversible redox waves appeared, indicating that the presence of GR-TiO₂ nanocomposite on the electrode surface could facilitate the electron transfer rate between the electroactive center of Hb and the substrate electrode. Hb modified electrode showed excellent electrocatalytic activity to the reduction of trichloroacetic acid in the concentration range from 0.6 to 21.0 mmol L⁻¹. These results indicated that GR-TiO₂ nanocomposite could be a friendly biocompatible interface for immobilizing biomolecules and keeping their native structure. The fabricated biosensor displayed the advantages such as high sensitivity, good reproducibility and long-term stability. Copyright © 2012 Elsevier B.V. All rights reserved.

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

Thermal batteries: A technology review and future directions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guidotti, R.A.

Thermally activated (``thermal``) batteries have been used for ordnance applications (e.g., proximity fuzes) since World War II and, subsequent to that, in nuclear weapons. This technology was developed by the Germans as a power source for their V2 rockets. It was obtained by the Allies by interrogation of captured German scientists after the war. The technology developed rapidly from the initial primitive systems used by the Germans to one based on Ca/CaCrO{sub 4}. This system was used very successfully into the late 1970s, when it was replaced by the Li-alloy/FeS{sub 2} electrochemical system. This paper describes the predominant electrochemical couplesmore » that have been used in thermal batteries over the years. Major emphasis is placed on the chemistry and electrochemistry of the Ca/CaCrO{sub 4} and Li-alloy/FeS{sub 2} systems. The reason for this is to give the reader a better appreciation for the advances in thermal-battery technology for which these two systems are directly responsible. Improvements to date in the current Li-alloy/FeS{sub 2} and related systems are discussed and areas for possible future research and development involving anodes, cathodes, electrolytes, and insulations are outlined. New areas where thermal-battery technology has potential applications are also examined.« less

Investigating the thermostability of succinate: quinone oxidoreductase enzymes by direct electrochemistry at SWNTs-modified electrodes and FTIR spectroscopy

PubMed Central

Melin, Frederic; Noor, Mohamed R.; Pardieu, Elodie; Boulmedais, Fouzia; Banhart, Florian; Cecchini, Gary; Soulimane, Tewfik

2015-01-01

Succinate Quinone reductases (SQRs) are the enzymes which couple the oxidation of succinate and the reduction of quinones in the respiratory chain of prokaryotes and eukaryotes. We compare herein the temperature-dependent activity and structural stability of two SQRs, the first one from the mesophilic bacterium E. coli and the second one from the thermophilic bacterium T. thermophilus by a combined electrochemical and infrared spectroscopy approach. Direct electron transfer was achieved with the full membrane protein complexes at SWNTs-modified electrodes. The possible structural factors which contribute to the temperature-dependent activity of the enzymes and to the thermostability of the T. thermophiles SQR in particular, are discussed. PMID:25139263

Study of the Tributyl Phosphate--30 Percent Dodecane Solvent; ETUDE DU SOLVANT PHOSPHATE TRIBUTYLIQUE 30 PERCENT--DODECANE (in French)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leroy, P.

1967-07-01

This study, originating mainly from a literature survey, gives the principal chemical and physical features of the tributyl-phosphate (TBP) agent diluted at 30 volumes per cent in dodecane. The mixture is a very commonly used extractant in nuclear fuel processing. In this paper, the main following points are reported: -) the components (TBP and diluents) -) the TBP-diluents systems (non-loaded), -) the TBP-diluents-water systems, -) TBP-diluents-water-nitric acid systems, and -) industrial solvents. (author) [French] Cette etude, d'origine bibliographique, regroupe les caracteristiques physico-chimiques essentielles du phosphate tributylique (TBP) dilue a 30% en volume dans du dodecane. Ce melange constitue un agentmore » d'extraction tres utilise dans le traitement des combustibles nucleaires. Les principaux points traites sont les suivants: -) les constituants (TBP et diluants), -) les systemes TBP-diluants non charges, -) les systemes TBP-diluants-eau, -) les systemes TBP-diluants-eau-acide nitrique, et -) les solvants industriels. (auteur)« less

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.

Opto-electrochemical In Situ Monitoring of the Cathodic Formation of Single Cobalt Nanoparticles.

PubMed

Brasiliense, Vitor; Clausmeyer, Jan; Dauphin, Alice L; Noël, Jean-Marc; Berto, Pascal; Tessier, Gilles; Schuhmann, Wolfgang; Kanoufi, Fréderic

2017-08-21

Single-particle electrochemistry at a nanoelectrode is explored by dark-field optical microscopy. The analysis of the scattered light allows in situ dynamic monitoring of the electrodeposition of single cobalt nanoparticles down to a radius of 65 nm. Larger sub-micrometer particles are directly sized optically by super-localization of the edges and the scattered light contains complementary information concerning the particle redox chemistry. This opto-electrochemical approach is used to derive mechanistic insights about electrocatalysis that are not accessible from single-particle electrochemistry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct voltammetric specific recognition of dopamine using AlIII-DA complexes at the hanging mercury drop electrode.

PubMed

Zhang, Fuping; Zhang, Min; Cheng, Jiongjia; Yang, Li; Ji, Ming; Bi, Shuping

2007-11-01

In this paper, we firstly report the direct voltammetric recognition and determination of dopamine (DA) by using Al(III)-DA complexes at the hanging mercury drop electrode (HMDE). A new sensitive cathodic peak of Al(III)-DA can be detected at -900 mV (vs. SCE) in 0.1 M NH(4)Cl-NH(3).H(2)O-0.1 M KCl buffer solution at pH 8.5. This unique -900 mV cathodic peak arises from the specific interaction between Al(III) and DA on the HMDE, whereas other substances with similar structures, such as L-dopa, epinephrine (EP), norepinephrine (NE), catechols, caffeic acid (CA), trihydric phenols and tiron, do not yield any new peak on the voltammograms in the potential range from -100 to -1200 mV when Al(III) is added. The distinct voltammetric characteristic of the recognition of DA can effectively inhibit the interferences of both ascorbic acid and uric acid in the DA determination by the direct electrochemistry, which is a major difficulty when a solid electrode is used. The proposed method can be anticipated as an effective means for the recognition of DA in the elucidation of the mechanisms of Parkinson's disease (PD) and Alzheimer's disease (AD) in the presence of Al(III).

Electrochemistry of lunar rocks

NASA Technical Reports Server (NTRS)

Lindstrom, D. J.; Haskin, L. A.

1979-01-01

Electrolysis of silicate melts has been shown to be an effective means of producing metals from common silicate materials. No fluxing agents need be added to the melts. From solution in melts of diopside (CaMgSi2O6) composition, the elements Si, Ti, Ni, and Fe have been reduced to their metallic states. Platinum is a satisfactory anode material, but other cathode materials are needed. Electrolysis of compositional analogs of lunar rocks initially produces iron metal at the cathode and oxygen gas at the anode. Utilizing mainly heat and electricity which are readily available from sunlight, direct electrolysis is capable of producing useful metals from common feedstocks without the need for expendable chemicals. This simple process and the products obtained from it deserve further study for use in materials processing in space.

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

Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Feng; Liu, Yijin; Yu, Xiqian

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

Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries

DOE PAGES

Lin, Feng; Liu, Yijin; Yu, Xiqian; ...

2017-08-30

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

Etude experimentale des excitations topologiques de l'effet Hall quantique a nu = 1 dans les heterostructures semiconductrices a double puits quantique

NASA Astrophysics Data System (ADS)

Charlebois, Serge

De nombreux travaux theoriques et experimentaux ont ete publies sur les excitations topologiques de gaz electroniques bidimensionnels (GE2D), appellees skyrmions, dans le regime de l'effet Hall quantique a remplissage unitaire. On attend des excitations semblables appellees bimerons dans les systemes formes de deux GE2D couples. Contrairement au cas des GE2D simples, aucune experience n'a, a notre connaissance, presente la mesure d'une propriete specifique aux bimerons. Nous presentons dans cette these des travaux experimentaux ayant pour objectif l'etude d'excitations topologiques dans les heterostructures a double puits quantique. Une manifestation attendue (les bimerons est la presence d'une anisotropie dans la conductivite a travers une constriction. Nous avons concu un dispositif original a point de contact a trois grilles non-coplanaires. Ce dispositif a trois grilles a la particularite de permettre la creation d'une constriction etroite dans le double GE2D tout en permettant l'equilibrage de la densite electronique entre les deux puits dans l'etroit canal de conduction. Nous avons fabrique ce dispositif de taille submicronique par electrolithographie sur des heterostructures a double puits. Les dispositifs ainsi fabriques ont ete etudies a basse temperature (0.3K) et ont montre un fonctionnement conforme aux attentes. Les travaux n'ont pas permis de mettre en evidence une anisotropie de transport revelatrice de l'existence de bimerons. Cette these est a notre connaissance la premiere etude experimentale visant la realisation de l'experience d'anisotropie de transport et est ainsi une contribution significative a l'avancement des connaissances dans ce domaine. Les travaux theoriques que nous presentons ont permis de montrer l'effet des excitations topologiques sur la capacite grille-GE2D du systeme. Ces travaux ouvrent la voie de la detection des bimerons par l'intermediaire de la mesure de la capacite grille-GE2D ou encore de la susceptibilite electrique du

Etude hyperfrequence et ultrasonore des supraconducteurs organiques kappa-(ET)(2)X (X = copper(thiocyanogen), copper[N(CN)(2)]bromine)

NASA Astrophysics Data System (ADS)

Frikach, Kamal

2001-09-01

Dans ce travail je presente une etude de l'impedance de surface, ainsi que de l'attenuation et la variation de la vitesse ultrasonores dans les etats normal et supraconducteur sur les composes organiques k-(ET)2X (X = Cu(SCN) 2, Cu[N(CN)2]Br). A partir des mesures d'impedance de surface, les deux composantes sigma 1 et sigma2 de la conductivite complexe sont extraites en utilisant le modele de Drude. Ces mesures montrent que la symetrie du parametre d'ordre dans ces composes est differente de celle du cas BCS. Afin de comprendre le profil de sigma1 (T) nous avons etudie les fluctuations supraconductrices a partir de la paraconductivite sigma'( T). Cette etude est rendue possible grace a la structure quasi-2D des composes k-(ET)2X dans lesquelles les fluctuations supraconductrices sont fortes. Ces dernieres sont observees sur deux decades de temperatures dans le Cu(SCN)2. L'application du modele de Aslamazov-Larkin 2D et 3D montre la possibilite du passage du regime 2D a haute temperature au regime 3D au voisinage de Tc. En se basant sur ce resultat, nous avons calcule la paraconductivite en utilisant une approche a l'ordre d'une boucle a partir du modele de Lawrence-Doniach. En tenant compte de la correction par la self energie dans la limite dynamique (17 GHz), l'ajustement de la paraconductivite calculee est en bon accord avec les donnees experimentales. Le couplage interplan obtenu est compatible avec le caractere quasi-2D des composes organiques. Le temps de relaxation des quasi-particules dans l'etat supraconducteur est ensuite extrait pour la premiere fois dans ces composes dont le comportement en fonction de la temperature est compatible avec la presence des noeuds dans le gap. Dans l'etat normal, la variation de la vitesse ultrasonore presente un comportement anormal caracterise par un fort ramollissement a T = 38 K et 50 K dans k-(ET) 2Cu(SCN)2 et k-(ET)2Cu[N(CN) 2]Br respectivement dont l'amplitude est independante du champ magnetique jusqu'a H = Hc 2

Electrochemistry of mixed-metal bimetallic complexes containing the pentacyanoferrate(II) or pentaammineruthenium(II) metal center

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, K.J.; Lee, L.; Mabbott, G.A.

1983-03-30

The electrochemistry of a series of mixed-metal bimetallic complexes of the type B/sub 5/MLM'B'/sub 5/, where B/sub 5/M = (CNN)/sub 5/Fe/sup II/ or (NH/sub 3/)/sub 5/Ru/sup II/, L = pyrazine, 4,4'-bipyridine, or 4-cyanopyridine, M'B'/sub 5/ = Rh/sup III/(NH/sub 3/)/sub 5/ or Co/sup III/(CN)/sub 5/, is reported. The bimetallic complexes all have metal-to-ligand charge-transfer (MLCT) bands associated with the M-B unit (d/sub ..pi../M ..-->.. p/sub ..pi../*L). The effect of the remote metal center, M'B'/sub 5/, is to function as a Lewis acid, shifting the MLCT maximum to lower energy and shifting the M/sup III///sup II/ reduction potential more positive with respectmore » to free B/sub 5/ML. The remote metal influence is attenuated by longer bridging ligands and by reduced ..pi..-overlap. A comparison of the electrochemical data of the mixed-valence Fe(II)/Fe(III) and Ru(II)/Ru(III) complexes to the mixed-metal Fe(II)/Co(III) and Ru(II)/Rh(III) complexes has enabled a quantitative measure of the stabilization due to electron delocalization in the mixed-valence complexes. The results show that electron delocalization is greater for the ruthenium complexes than for the iron complexes, is a small contributor to the total stabilization of the mixed-valence state, and even in ruthenium drops off rapidly as the length of the bridge increases.« less

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

NASA Astrophysics Data System (ADS)

Martinez, Nicolas

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

Using porphyrin-amino acid pairs to model the electrochemistry of heme proteins: experimental and theoretical investigations.

PubMed

Samajdar, Rudra N; Manogaran, Dhivya; Yashonath, S; Bhattacharyya, Aninda J

2018-04-18

Quasi reversibility in electrochemical cycling between different oxidation states of iron is an often seen characteristic of iron containing heme proteins that bind dioxygen. Surprisingly, the system becomes fully reversible in the bare iron-porphyrin complex: hemin. This leads to the speculation that the polypeptide bulk (globin) around the iron-porphyrin active site in these heme proteins is probably responsible for the electrochemical quasi reversibility. To understand the effect of such polypeptide bulk on iron-porphyrin, we study the interaction of specific amino acids with the hemin center in solution. We choose three representative amino acids-histidine (a well-known iron coordinator in bio-inorganic systems), tryptophan (a well-known fluoroprobe for proteins), and cysteine (a redox-active organic molecule). The interactions of these amino acids with hemin are studied using electrochemistry, spectroscopy, and density functional theory. The results indicate that among these three, the interaction of histidine with the iron center is strongest. Further, histidine maintains the electrochemical reversibility of iron. On the other hand, tryptophan and cysteine interact weakly with the iron center but disturb the electrochemical reversibility by contributing their own redox active processes to the system. Put together, this study attempts to understand the molecular interactions that can control electrochemical reversibility in heme proteins. The results obtained here from the three representative amino acids can be scaled up to build a heme-amino acid interaction database that may predict the electrochemical properties of any protein with a defined polypeptide sequence.

Electrochemistry, surface plasmon resonance, and quartz crystal microbalance: an associative study on cytochrome c adsorption on pyridine tail-group monolayers on gold.

PubMed

Paulo, Tércio de F; de Sousa, Ticyano P; de Abreu, Dieric S; Felício, Nathalie H; Bernhardt, Paul V; Lopes, Luiz G de F; Sousa, Eduardo H S; Diógenes, Izaura C N

2013-07-25

Quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and electrochemistry techniques were used to study the electron-transfer (ET) reaction of cytochrome c (Cyt c) on gold surfaces modified with thionicotinamide, thioisonicotinamide, 4-mercaptopyridine, 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol, 5-phenyl-1,3,4-oxadiazole-2-thiol, 4,4'-bipyridine, and 4,4'-dithiopyridine. The electrochemical results showed that the ET process is complex, being chiefly diffusional with steps depending on the orientation of the pyridine or phenyl tail group of the modifiers. The correlation between the electrochemical results and those acquired by SPR and QCM indicated the presence of an adlayer of Cyt c adsorbed on the thiolate SAMs. This adlayer, although being not electroactive, is essential to assess the ET reaction of Cyt c in solution. The results presented in this work are consistent with the statement (Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Electroanal. Chem. 1995, 394, 149-154) that the ET reaction of Cyt c can be explained in terms of the through-bond tunneling mechanism.

Le transfert de connaissances entre les mathematiques et les sciences. Une etude exploratoire aupres d'eleves de 4e secondaire

NASA Astrophysics Data System (ADS)

Samson, Ghislain

2003-06-01

Au moment ou dans plusieurs pays on travaille a refondre les programmes d'etudes, tant au primaire qu'au secondaire, l'interet pour le transfert renait. Un des concepts fondamentaux en apprentissage consiste en l'habilete a reutiliser de facon consciente et efficace un acquis d'une situation a une autre situation. Cette recherche emane de preoccupations professionnelles au moment ou le chercheur etait enseignant au secondaire. Au cours de ces annees, il lui a ete possible de constater que plusieurs eleves percevaient difficilement les liens presents entre les disciplines mathematiques et scientifiques. Des travaux en psychologie cognitive et plus particulierement selon une perspective du traitement de l'information ont servi de cadre de reference pour evaluer et analyser les capacites de transfert aupres d'eleves de 4e secondaire. Ce cadre de reference permet de formuler le principal objectif qui est de mieux comprendre le processus de transfert chez des eleves en situation de resolution de problemes scientifiques. Cette these s'interesse donc au transfert en tant que phenomene important du processus d'apprentissage au sens de l'integration. La methode de recherche choisie, de nature qualitative, est principalement axee sur l'evaluation de la capacite a transferer des connaissances lors d'une epreuve et d'un entretien. Pour evaluer ce potentiel de transfert, nous avons elabore deux outils: une epreuve en mathematiques et en sciences et un guide d'entretien. Pour la passation de l'epreuve, le chercheur a pu compter sur la collaboration de 130 sujets provenant de deux ecoles. L'entretien complete la prise de donnees avec 13 sujets ayant accepte de poursuivre l'etude. Les donnees recueillies par ces instruments font ensuite l'objet d'une analyse de contenu. En premier lieu, les verbatims de l'epreuve et de l'entretien ont ete transcrits, puis codifies. La correction des reponses fournies pour les problemes resolus s'est faite a partir d'une grille d

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

PubMed

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

2015-11-30

Currently, the primary technique employed in circuit-level study of the brain is electrophysiology, recording local field or action potentials (LFPs or APs). However most communication between neurons is chemical and the relationship between electrical activity within neurons and chemical signaling between them is not well understood in vivo, particularly for molecules that signal at least in part by non-synaptic transmission. We describe a multi-contact array and accompanying head stage circuit that together enable concurrent electrophysiological and electrochemical recording. The array is small (<200 μm) 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. 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. Our system offers the possibility for conducting in vivo studies in a range of species that examine the relationship between the electrical activity of neurons and their chemical environment, with exquisite spatial and temporal precision. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

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

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.

Chemical and Electrochemical Studies in Ionic Liquids

DTIC Science & Technology

1990-01-12

Electrochemistry and Witchcraft ", Gordon Research Conference on Electrochemistry", Santa Barbara, CA, January, 1985. OR. A. Osteryoung, ’An Introduction to...Temperature Chloroaluminate Ionic Liquids: Chemistry, Electrochemistry and Witchcraft ", Chemistry Department Colloquium, University of Alabama...Tuscaloosa, Alabama, December 1, 1988. OR. A. Osteryoung, "Ambient Temperature Chloroaluminate Ionic Liquids: Chemistry, Electrochemistry and Witchcraft

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.

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

PubMed

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

2013-11-07

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

Nanoscale methods for single-molecule electrochemistry.

PubMed

Mathwig, Klaus; Aartsma, Thijs J; Canters, Gerard W; Lemay, Serge G

2014-01-01

The development of experiments capable of probing individual molecules has led to major breakthroughs in fields ranging from molecular electronics to biophysics, allowing direct tests of knowledge derived from macroscopic measurements and enabling new assays that probe population heterogeneities and internal molecular dynamics. Although still somewhat in their infancy, such methods are also being developed for probing molecular systems in solution using electrochemical transduction mechanisms. Here we outline the present status of this emerging field, concentrating in particular on optical methods, metal-molecule-metal junctions, and electrochemical nanofluidic devices.

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

PubMed

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

2016-02-15

The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and 7-ethoxycoumarin with phase I metabolites of the same compounds produced in vitro by human liver microsomes (HLM). Reaction products were analysed by UHPLC-MS. TiO2 photocatalysis simulated the in vitro phase I metabolism in HLM more comprehensively than did EC-Fenton or EC. Even though TiO2 photocatalysis, EC-Fenton and EC do not allow comprehensive prediction of phase I metabolism, all three methods produce several important metabolites without the need for demanding purification steps to remove the biological matrix. Importantly, TiO2 photocatalysis produces aliphatic and aromatic hydroxylation products where direct EC fails. Furthermore, TiO2 photocatalysis is an extremely rapid, simple and inexpensive way to generate oxidation products in a clean matrix and the reaction can be simply initiated and quenched by switching the UV lamp on/off. Copyright © 2015 Elsevier B.V. All rights reserved.

Modern Data Analysis techniques in Noise and Vibration Problems

DTIC Science & Technology

1981-11-01

Hilbert l’une de l’autre. Cette propriete se retrouve dans l’etude de la causalite : ce qui de- finit un critere pratique caracterisant un signal donc, par...entre Ie champ direct et Ie champ reflechi se caracterisent loca- lement par l’existence de frequences pour lesquelles l’interference est totale

Goals.

ERIC Educational Resources Information Center

Phillips, David A.; Phillips, Prudence

1985-01-01

Presents two discussions which focus on the rationale for and goals of teaching electrochemistry at high school and college levels. The first is "Electrochemistry" by Ronald Perkins and the second is "Goals in Teaching Electrochemistry" by J. T. Maloy. (JN)

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

French Research in Acoustics and Signal Processing: Report on Introductory Visit

DTIC Science & Technology

1986-05-01

CEPHAG (Centre d’Etude des Phenomenes Aleatoires et Geophysiques ), which is associated with the Institut National Polytechnique at Grenoble. We were...measurement programs. Centre d’Etude des Phenomenes Aleatoires et Geophysiques (CEPHAG), Institut National Polytechnique, Universite de Grenoble, 23 May...69288 Lyon Cedex, France, Tel 72.32.50.67. CENTRE D’ETUDE DES PHENOMENES ALEATOIRES ET GEOPHYSIQUES (CEPHAG), Grenoble. Prof. J. L. Lacoume

One-step synthesis of large-scale graphene film doped with gold nanoparticles at liquid-air interface for electrochemistry and Raman detection applications.

PubMed

Zhang, Panpan; Huang, Ying; Lu, Xin; Zhang, Siyu; Li, Jingfeng; Wei, Gang; Su, Zhiqiang

2014-07-29

We demonstrated a facile one-step synthesis strategy for the preparation of a large-scale reduced graphene oxide multilayered film doped with gold nanoparticles (RGO/AuNP film) and applied this film as functional nanomaterials for electrochemistry and Raman detection applications. The related applications of the fabricated RGO/AuNP film in electrochemical nonenzymatic H2O2 biosensor, electrochemical oxygen reduction reaction (ORR), and surface-enhanced Raman scattering (SERS) detection were investigated. Electrochemical data indicate that the H2O2 biosensor fabricated by RGO/AuNP film shows a wide linear range, low limitation of detection, high selectivity, and long-term stability. In addition, it was proved that the created RGO/AuNP film also exhibits excellent ORR electrochemical catalysis performance. The created RGO/AuNP film, when serving as SERS biodetection platform, presents outstanding performances in detecting 4-aminothiophenol with an enhancement factor of approximately 5.6 × 10(5) as well as 2-thiouracil sensing with a low concentration to 1 μM. It is expected that this facile strategy for fabricating large-scale graphene film doped with metallic nanoparticles will spark inspirations in preparing functional nanomaterials and further extend their applications in drug delivery, wastewater purification, and bioenergy.

Preparation and structure of Na2Ag5Fe3(P2O7)4 -Ag metal composite: Insights on electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiman; Marschilok, Amy C.; Takeuchi, Esther S.

ABSTRACT Ag 7Fe 3(P 2O 7) 4is a 3D structured material which has been recently studied as a possible cathode material for lithium batteries. Notably, Na 7Fe 3(P 2O 7) 4is reported to be a fast-ion conductor, yet poor electrical conductor. Here, partial replacement of Na +for Ag +yielded Na 2Ag 5Fe 3(P 2O 7) 4pyrophosphate framework where the formation of Ag metal is proposed to increase the intrinsic low electrical conductivity of this polyanion electrode. Specifically, the Ag 5Na 2Fe 3(P 2O 7) 4-Ag composite is synthesized via chemical reduction of Ag 7Fe 3(P 2O 7) 4using NaBH 4.more » The occupancy of Ag +and Na +in each site was determined via Rietveld analysis of the diffraction pattern. Electrochemistry of the Ag 5Na 2Fe 3(P 2O 7) 4-Ag metal composite was explored with voltammetry and galvanostatic charge/discharge cycling. The Ag 5Na 2Fe 3(P 2O 7) 4-Ag metal composite electrodes displayed good rate capability assisted by the presence of Ag metal from the chemical reduction and in-situ electrochemical formation of a Ag conductive network.« less

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

PubMed

Repp, B H

1999-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Etude de la dynamique des porteurs dans des nanofils de silicium par spectroscopie terahertz

NASA Astrophysics Data System (ADS)

Beaudoin, Alexandre

Ce memoire presente une etude des proprietes de conduction electrique et de la dynamique temporelle des porteurs de charges dans des nanofils de silicium sondes par rayonnement terahertz. Les cas de nanofils de silicium non intentionnellement dopes et dopes type n sont compares pour differentes configurations du montage experimental. Les mesures de spectroscopie terahertz en transmission montre qu'il est possible de detecter la presence de dopants dans les nanofils via leur absorption du rayonnement terahertz (˜ 1--12 meV). Les difficultes de modelisation de la transmission d'une impulsion electromagnetique dans un systeme de nanofils sont egalement discutees. La detection differentielle, une modification au systeme de spectroscopie terahertz, est testee et ses performances sont comparees au montage de caracterisation standard. Les instructions et des recommendations pour la mise en place de ce type de mesure sont incluses. Les resultats d'une experience de pompe optique-sonde terahertz sont egalement presentes. Dans cette experience, les porteurs de charge temporairement crees suite a l'absorption de la pompe optique (lambda ˜ 800 nm) dans les nanofils (les photoporteurs) s'ajoutent aux porteurs initialement presents et augmentent done l'absorption du rayonnement terahertz. Premierement, l'anisotropie de l'absorption terahertz et de la pompe optique par les nanofils est demontree. Deuxiemement, le temps de recombinaison des photoporteurs est etudie en fonction du nombre de photoporteurs injectes. Une hypothese expliquant les comportements observes pour les nanofils non-dopes et dopes-n est presentee. Troisiemement, la photoconductivite est extraite pour les nanofils non-dopes et dopes-n sur une plage de 0.5 a 2 THz. Un lissage sur la photoconductivite permet d'estimer le nombre de dopants dans les nanofils dopes-n. Mots-cles: nanofil, silicium, terahertz, conductivite, spectroscopie, photoconductivite.

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

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–y Mn y O 4 (0.4 ≤ y ≤ 1)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

The thermal conversion of chemically delithiated layered Li 0.5Ni 1-yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2-yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied in lithium-ion cells. Amore » bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. The study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1)

DOE PAGES

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

2015-10-28

The thermal conversion of chemically delithiated layered Li 0.5Ni 1–yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated in this paper. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied inmore » lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. Finally, the study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kan, Wang Hay; Huq, Ashfia; Manthiram, Arumugam

The thermal conversion of chemically delithiated layered Li 0.5Ni 1–yMn yO 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2–yMn yO 4 (0.4 ≤ y ≤ 1) has been systematically investigated in this paper. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied inmore » lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. Finally, the study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.« less

Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy

DOE PAGES

Harrison, Katharine L.; Zavadil, Kevin R.; Hahn, Nathan T.; ...

2017-11-07

To understand the mechanism that controls low-aspect-ratio lithium deposition morphologies for Li-metal anodes in batteries, we conducted direct visualization of Li-metal deposition and stripping behavior through nanoscale in situ electrochemical scanning transmission electron microscopy (EC-STEM) and macroscale-cell electrochemistry experiments in a recently developed and promising solvate electrolyte, 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane. In contrast to published coin cell studies in the same electrolyte, our experiments revealed low Coulombic efficiencies and inhomogeneous Li morphology during in situ observation. In addition, we conclude that this discrepancy in Coulombic efficiency and morphology of the Li deposits was dependent on the presence ofmore » a compressed lithium separator interface, as we have confirmed through macroscale (not in the transmission electron microscope) electrochemical experiments. Our data suggests that cell compression changed how the solid-electrolyte interphase formed, which is likely responsible for improved morphology and Coulombic efficiency with compression. Furthermore, during the in situ EC-STEM experiments, we observed direct evidence of nanoscale self-discharge in the solvate electrolyte (in the state of electrical isolation). This self-discharge was duplicated in the macroscale, but it was less severe with electrode compression, likely due to a more passivating and corrosion-resistant solid-electrolyte interphase formed in the presence of compression. By combining the solvate electrolyte with a protective LiAl 0.3S coating, we show that the Li nucleation density increased during deposition, leading to improved morphological uniformity. In conclusion, self-discharge was suppressed during rest periods in the cycling profile with coatings present, as evidenced through EC-STEM and confirmed with coin cell data.« less

Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy.

PubMed

Harrison, Katharine L; Zavadil, Kevin R; Hahn, Nathan T; Meng, Xiangbo; Elam, Jeffrey W; Leenheer, Andrew; Zhang, Ji-Guang; Jungjohann, Katherine L

2017-11-28

To understand the mechanism that controls low-aspect-ratio lithium deposition morphologies for Li-metal anodes in batteries, we conducted direct visualization of Li-metal deposition and stripping behavior through nanoscale in situ electrochemical scanning transmission electron microscopy (EC-STEM) and macroscale-cell electrochemistry experiments in a recently developed and promising solvate electrolyte, 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane. In contrast to published coin cell studies in the same electrolyte, our experiments revealed low Coulombic efficiencies and inhomogeneous Li morphology during in situ observation. We conclude that this discrepancy in Coulombic efficiency and morphology of the Li deposits was dependent on the presence of a compressed lithium separator interface, as we have confirmed through macroscale (not in the transmission electron microscope) electrochemical experiments. Our data suggests that cell compression changed how the solid-electrolyte interphase formed, which is likely responsible for improved morphology and Coulombic efficiency with compression. Furthermore, during the in situ EC-STEM experiments, we observed direct evidence of nanoscale self-discharge in the solvate electrolyte (in the state of electrical isolation). This self-discharge was duplicated in the macroscale, but it was less severe with electrode compression, likely due to a more passivating and corrosion-resistant solid-electrolyte interphase formed in the presence of compression. By combining the solvate electrolyte with a protective LiAl 0.3 S coating, we show that the Li nucleation density increased during deposition, leading to improved morphological uniformity. Furthermore, self-discharge was suppressed during rest periods in the cycling profile with coatings present, as evidenced through EC-STEM and confirmed with coin cell data.

Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harrison, Katharine L.; Zavadil, Kevin R.; Hahn, Nathan T.

To understand the mechanism that controls low-aspect-ratio lithium deposition morphologies for Li-metal anodes in batteries, we conducted direct visualization of Li-metal deposition and stripping behavior through nanoscale in situ electrochemical scanning transmission electron microscopy (EC-STEM) and macroscale-cell electrochemistry experiments in a recently developed and promising solvate electrolyte, 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane. In contrast to published coin cell studies in the same electrolyte, our experiments revealed low Coulombic efficiencies and inhomogeneous Li morphology during in situ observation. In addition, we conclude that this discrepancy in Coulombic efficiency and morphology of the Li deposits was dependent on the presence ofmore » a compressed lithium separator interface, as we have confirmed through macroscale (not in the transmission electron microscope) electrochemical experiments. Our data suggests that cell compression changed how the solid-electrolyte interphase formed, which is likely responsible for improved morphology and Coulombic efficiency with compression. Furthermore, during the in situ EC-STEM experiments, we observed direct evidence of nanoscale self-discharge in the solvate electrolyte (in the state of electrical isolation). This self-discharge was duplicated in the macroscale, but it was less severe with electrode compression, likely due to a more passivating and corrosion-resistant solid-electrolyte interphase formed in the presence of compression. By combining the solvate electrolyte with a protective LiAl 0.3S coating, we show that the Li nucleation density increased during deposition, leading to improved morphological uniformity. In conclusion, self-discharge was suppressed during rest periods in the cycling profile with coatings present, as evidenced through EC-STEM and confirmed with coin cell data.« less

Advances in X-Ray Simulator Technology

DTIC Science & Technology

1995-07-01

d’Etudes de Gramat ; I. Vitkovitsky, Logicon RDA INTRODUCTION DNA’s future x-ray simulators are based upon inductive energy storage, a technology which...switch. SYRINX, a proposed design to be built by the Centre d’Etudes de Gramat (CEG) in France would employ a modular approach, possibly with a...called SYRINX, would be built at the Centred’ Etudes de Gramat (CEG). It would employ a modular.long conduction time current source to drive a PRS

Synthetic Control of Crystallite Size of Silver Vanadium Phosphorous Oxide (Ag 0.50VOPO 4·1.9H 2O): Impact on Electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huie, Matthew M.; Marschilok, Amy C.; Takeuchi, Esther S.

Here, this report describes a synthetic approach to control the crystallite size of silver vanadium phosphorous oxide, Ag 0.50VOPO 4·1.9H 2O, and the impact on electrochemistry in lithium based batteries. Ag 0.50VOPO 4·1.9H 2O was synthesized using a stirred hydrothermal method over a range of temperatures. X-ray diffraction (XRD) was used to confirm the crystalline phase and the crystallite size sizes of 11, 22, 38, 40, 49, and 120 nm. Particle shape was plate-like with edges <1 micron to >10 microns. Under galvanostatic reduction the samples with 22 nm crystallites and 880 nm particles produced the highest capacity, ~25% moremore » capacity than the 120 nm sample. Notably, the 11 nm sample resulted in reduced delivered capacity and higher resistance consistent with increased grain boundaries contributing to resistance. Under intermittent pulsing ohmic resistance decreased with increasing crystallite size from 11 nm to 120 nm implying that electrical conduction within a crystal is more facile than between crystallites and across grain boundaries. Finally, this systematic study of material dimension shows that crystallite size impacts deliverable capacity as well as cell resistance where both interparticle and intraparticle transport are important.« less

Synthetic Control of Crystallite Size of Silver Vanadium Phosphorous Oxide (Ag 0.50VOPO 4·1.9H 2O): Impact on Electrochemistry

DOE PAGES

Huie, Matthew M.; Marschilok, Amy C.; Takeuchi, Esther S.; ...

2017-04-12

Here, this report describes a synthetic approach to control the crystallite size of silver vanadium phosphorous oxide, Ag 0.50VOPO 4·1.9H 2O, and the impact on electrochemistry in lithium based batteries. Ag 0.50VOPO 4·1.9H 2O was synthesized using a stirred hydrothermal method over a range of temperatures. X-ray diffraction (XRD) was used to confirm the crystalline phase and the crystallite size sizes of 11, 22, 38, 40, 49, and 120 nm. Particle shape was plate-like with edges <1 micron to >10 microns. Under galvanostatic reduction the samples with 22 nm crystallites and 880 nm particles produced the highest capacity, ~25% moremore » capacity than the 120 nm sample. Notably, the 11 nm sample resulted in reduced delivered capacity and higher resistance consistent with increased grain boundaries contributing to resistance. Under intermittent pulsing ohmic resistance decreased with increasing crystallite size from 11 nm to 120 nm implying that electrical conduction within a crystal is more facile than between crystallites and across grain boundaries. Finally, this systematic study of material dimension shows that crystallite size impacts deliverable capacity as well as cell resistance where both interparticle and intraparticle transport are important.« less

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

PubMed

Repp, B H

1998-08-01

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

Fabrication of an electrochemical platform based on the self-assembly of graphene oxide-multiwall carbon nanotube nanocomposite and horseradish peroxidase: direct electrochemistry and electrocatalysis

NASA Astrophysics Data System (ADS)

Zhang, Qian; Yang, Shaojun; Zhang, Jing; Zhang, Ling; Kang, Pingli; Li, Jinghong; Xu, Jingwei; Zhou, Hua; Song, Xi-Ming

2011-12-01

A novel hybrid nanomaterial (GO-MWNTs) was explored based on the self-assembly of multiwall carbon nanotubes (MWNTs) and graphene oxide (GO). Compared with pristine MWNTs, such a nanocomposite could be well dispersed in aqueous solution and exhibit a negative charge. Driven by the electrostatic interaction, positively charged horseradish peroxidase (HRP) could then be immobilized onto GO-MWNTs at the surface of a glassy carbon (GC) electrode to form a HRP/GO-MWNT/GC electrode under mild conditions. TEM was used to characterize the morphology of the GO-MWNT nanocomposite. UV-vis and FTIR spectra suggested that HRP was immobilized onto the hybrid matrix without denaturation. Furthermore, the immobilized HRP showed enhanced direct electron transfer for the HRP-Fe(III)/Fe(II) redox center. Based on the direct electron transfer of the immobilized HRP, the HRP/GO-MWNT/GC electrode exhibited excellent electrocatalytic behavior to the reduction of H2O2 and NaNO2, respectively. Therefore, GO-MWNTs could provide a novel and efficient platform for the immobilization and biosensing of redox enzymes, and thus may find wide potential applications in the fabrication of biosensors, biomedical devices, and bioelectronics.

Growth of Vertically Aligned ZnO Nanowire Arrays Using Bilayered Metal Catalysts

DTIC Science & Technology

2012-01-01

12] J. P. Liu, C. X. Guo, C. M. Li et al., “Carbon-decorated ZnO nanowire array: a novel platform for direct electrochemistry of enzymes and...cited. Vertically aligned, high-density ZnO nanowires (NWs) were grown for the first time on c-plane sapphire using binary alloys of Ni/Au or Cu/Au as...deleterious to the ZnO NW array growth. Significant improvement of the Au adhesion on the substrate was noted, opening the potential for direct

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

PubMed

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

2010-09-29

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

4TH International Topical Conference on High-Power Electron and Ion-Beam Research and Technology, held in Palaiseau, France, 29 June - 3 July 1981.

DTIC Science & Technology

1981-10-09

N. Camarcat (Centre d’Etudes de Valduc ) noted that the French were new in this field and presented the results of the experiments on LIB production...Beam Production on Low Impedance Generators" N. Camarcat et al. C.E.A.-D.A.M.-S.E.C.R. Centre d’Etudes de Valduc , France 7...Acceleration on the Thalie Generator" J. Cortella et al. C.E.A.-D.A.M.-S.E.C.R. Centre d’Etudes de Valduc , France ION PRODUCTION II "The Work on High

An electrochemical immunosensor based on chemical assembly of vertically aligned carbon nanotubes on carbon substrates for direct detection of the pesticide endosulfan in environmental water.

PubMed

Liu, Guozhen; Wang, Shuo; Liu, Jingquan; Song, Dandan

2012-05-01

A glassy carbon substrate was covalently modified with a mixed layer of 4-aminophenyl and phenyl via in situ electrografting of their aryldiazonium salts in acidic solutions. Single-walled carbon nanotubes (SWNTs) were covalently and vertically anchored on the electrode surface via the formation of amide bonds from the reaction between the amines located on the modified substrate and the carboxylic groups at the ends of the nanotubes. Ferrocenedimethylamine (FDMA) was subsequently attached to the ends of SWNTs through amide bonding followed by the attachment of an epitope, i.e., endosulfan hapten to which an antibody would bind. Association or dissociation of the antibody with the sensing interface causes a modulation of the ferrocene electrochemistry. Antibody-complexed electrodes were exposed to samples containing spiked endosulfan (unbound target analyte) in environment water and interrogated using the square wave voltammetry (SWV) technique. The modified sensing surfaces were characterized by atomic force microscopy, XPS, and electrochemistry. The fabricated electrochemical immunosensor can be successfully used for the detection of endosulfan over the range of 0.01-20 ppb by a displacement assay. The lowest detection limit of this immunosensor is 0.01 ppb endosulfan in 50 mM phosphate buffer at pH 7.0.

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

NASA Astrophysics Data System (ADS)

Grincourt, Yves

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

Strategies for "wiring" redox-active proteins to electrodes and applications in biosensors, biofuel cells, and nanotechnology.

PubMed

Nöll, Tanja; Nöll, Gilbert

2011-07-01

In this tutorial review the basic approaches to establish electrochemical communication between redox-active proteins and electrodes are elucidated and examples for applications in electrochemical biosensors, biofuel cells and nanotechnology are presented. The early stage of protein electrochemistry is described giving a short overview over electron transfer (ET) between electrodes and proteins, followed by a brief introduction into experimental procedures for studying proteins at electrodes and possible applications arising thereof. The article starts with discussing the electrochemistry of cytochrome c, the first redox-active protein, for which direct reversible ET was obtained, under diffusion controlled conditions and after adsorption to electrodes. Next, examples for the electrochemical study of redox enzymes adsorbed on electrodes and modes of immobilization are discussed. Shortly the experimental approach for investigating redox-active proteins adsorbed on electrodes is outlined. Possible applications of redox enzymes in electrochemical biosensors and biofuel cells working by direct ET (DET) and mediated ET (MET) are presented. Furthermore, the reconstitution of redox active proteins at electrodes using molecular wire-like units in order to "wire" the proteins to the electrode surface and possible applications in nanotechnology are discussed.

Computational assignment of redox states to Coulomb blockade diamonds.

PubMed

Olsen, Stine T; Arcisauskaite, Vaida; Hansen, Thorsten; Kongsted, Jacob; Mikkelsen, Kurt V

2014-09-07

With the advent of molecular transistors, electrochemistry can now be studied at the single-molecule level. Experimentally, the redox chemistry of the molecule manifests itself as features in the observed Coulomb blockade diamonds. We present a simple theoretical method for explicit construction of the Coulomb blockade diamonds of a molecule. A combined quantum mechanical/molecular mechanical method is invoked to calculate redox energies and polarizabilities of the molecules, including the screening effect of the metal leads. This direct approach circumvents the need for explicit modelling of the gate electrode. From the calculated parameters the Coulomb blockade diamonds are constructed using simple theory. We offer a theoretical tool for assignment of Coulomb blockade diamonds to specific redox states in particular, and a study of chemical details in the diamonds in general. With the ongoing experimental developments in molecular transistor experiments, our tool could find use in molecular electronics, electrochemistry, and electrocatalysis.

Mediatorless glucose biosensor and direct electron transfer type glucose/air biofuel cell enabled with carbon nanodots.

PubMed

Zhao, Mei; Gao, Yue; Sun, Junyong; Gao, Feng

2015-03-03

Utilization of carbon nanodots (CNDs), newcomers to the world of carbonaceous nanomaterials, in the electrochemistry realm has rarely been reported so far. In this study, CNDs were used as immobilization supports and electron carriers to promote direct electron transfer (DET) reactions of glucose oxidase (GOx) and bilirubin oxidase (BOD). At the CNDs electrode entrapped with GOx, a high rate constant (k(s)) of 6.28 ± 0.05 s(-1) for fast DET and an apparent Michaelis-Menten constant (K(M)(app)) as low as 0.85 ± 0.03 mM for affinity to glucose were found. By taking advantage of its excellent direct bioelectrocatalytic performances to glucose oxidation, a DET-based biosensor for glucose detection ranging from 0 to 0.64 mM with a high sensitivity of 6.1 μA mM(-1) and a limit of detection (LOD) of 1.07 ± 0.03 μM (S/N = 3) was proposed. Additionally, the promoted DET of BOD immobilized on CNDs was also observed and effectively catalyzed the reduction of oxygen to water at the onset potential of +0.51 V (vs Ag/AgCl). On the basis of the facilitated DET of these two enzymes at CNDs electrodes, a mediator-free DET-type glucose/air enzymatic biofuel cell (BFC), in which CNDs electrodes entrapped with GOx and BOD were employed for oxidizing glucose at the bioanode and reducing oxygen at the biocathode, respectively, was successfully fabricated. The constructed BFC displayed an open-circuit voltage (OCV) as high as 0.93 V and a maximum power density of 40.8 μW cm(-2) at 0.41 V. These important features of CNDs have implied to be promising materials for immobilizing enzymes and efficient platforms for elaborating bioelectrochemical devices such as biosensors and BFCs.

Electrochemistry of poly(3,4-ethylenedioxythiophene)-polyaniline/ Prussian blue electrochromic devices containing an ionic liquid based gel electrolyte film.

PubMed

Deepa, Melepurath; Awadhia, Arvind; Bhandari, Shweta

2009-07-21

Electrochromic devices based on poly(3,4-ethylenedioxythiophene) (PEDOT) as the cathodic coloring electrode and polyaniline (PANI) or Prussian blue (PB) as the counter electrode containing a highly conductive, self-supporting, distensible and transparent polymer-gel electrolyte film encapsulating an ionic liquid, 1-butyl-1-methylpyrrolidiniumbis-(trifluoromethylsulfonyl)imide, have been fabricated. Polarization, charge transfer and diffusion processes control the electrochemistry of the functional electrodes during coloration and bleaching and these phenomena differ when PEDOT and PANI/PB were employed alternately as working electrodes. While the electrochemical impedance response shows good similitude for PEDOT and PANI electrodes, the responses of PEDOT and PB were significantly different in the PEDOT-PB device, especially during reduction of PB, wherein the overall amplitude of the impedance response is enormous. Large values of the coloration efficiency maxima of 281 cm2 C(-1) (lambda = 583 nm) and 274 cm2 C(-1) (lambda = 602 nm), achieved at -1.0 and -1.5 V for the PEDOT PANI and PEDOT-PB devices have been correlated to the particularly low magnitude of charge transfer resistance and high polarization capacitance operative at the PEDOT ionic liquid based electrolyte interface at these dc potentials, thus allowing facile ion-transport and consequently resulting in enhanced absorption modulation. Moderately fast switching kinetics and the ability of these devices to sustain about 2500 cycles of clear-to-dark and dark-to-clear without incurring major losses in the optical contrast, along with the ease of construction of these cells in terms of high scalability and reproducibility of the synthetic procedure for fabrication of the electrochromic films and the ionic liquid based gel electrolyte film, are indicators of the promise these devices hold for practical applications like electrochromic windows and displays.

Prediction of biotransformation products of the fungicide fluopyram by electrochemistry coupled online to liquid chromatography-mass spectrometry and comparison with in vitro microsomal assays.

PubMed

Mekonnen, Tessema F; Panne, Ulrich; Koch, Matthias

2018-04-01

Biotransformation processes of fluopyram (FLP), a new succinate dehydrogenase inhibitor (SDHI) fungicide, were investigated by electrochemistry (EC) coupled online to liquid chromatography (LC) and electrospray mass spectrometry (ESI-MS). Oxidative phase I metabolite production was achieved using an electrochemical flow-through cell equipped with a boron-doped diamond (BDD) electrode. Structural elucidation and prediction of oxidative metabolism pathways were assured by retention time, isotopic patterns, fragmentation, and accurate mass measurements using EC/LC/MS, LC-MS/MS, and/or high-resolution mass spectrometry (HRMS). The results obtained by EC were compared with conventional in vitro studies by incubating FLP with rat and human liver microsomes (RLM, HLM). Known phase I metabolites of FLP (benzamide, benzoic acid, 7-hydroxyl, 8-hydroxyl, 7,8-dihydroxyl FLP, lactam FLP, pyridyl acetic acid, and Z/E-olefin FLP) were successfully simulated by EC/LC/MS. New metabolites including an imide, hydroxyl lactam, and 7-hydroxyl pyridyl acetic acid oxidative metabolites were predicted for the first time in our study using EC/LC/MS and liver microsomes. We found oxidation by dechlorination to be one of the major metabolism mechanisms of FLP. Thus, our results revealed that EC/LC/MS-based metabolic elucidation was more advantageous on time and cost of analysis and enabled matrix-free detection with valuable information about the mechanisms and intermediates of metabolism processes. Graphical abstract Oxidative metabolism of fluopyram.

The Microscale Synthesis and Electrochemistry of Low-Valent Mononuclear Complexes (h3-C3H5)Fe(CO)3 X (X = I, Br, Cl)

NASA Astrophysics Data System (ADS)

Mocellin, Enrico; Russell, Richard; Ravera, Mauro

1998-06-01

The experimental content of this paper will appeal to pedagogues and students who might be looking for new ideas that have an element of challenge. By combining experimental procedures which place microscale, chemical synthesis, and an inclusive, unified, product characterization in perspective, we have afforded the student the scope to obtain progressive, disciplined results and the opportunity to discuss these in the subsequent reporting. By this process, it is our experience that the students often identify with the practical work that is being undertaken, and they develop considerable empathy during their contribution to the "discovery" process that this laboratory program offers. The experimental work can be abbreviated to a single compound, subdivided into synthesis or electrochemistry, or extended to macroscale and other instrumental techniques of characterization, thus offering opportunities to accommodate time constraints, class results combination and discussion, and individual student enthusiasm. We believe that having to accept and/or constructively criticize sequential experimental results, collected by fellow students, mimics more realistically the practice of chemistry at the workplace and can build enthusiasm and elicit contagious fellowship from the class. All of these aspects can simply be achieved by utilizing the listed journals and references therein. Most importantly, it affords the students the opportunity to extricate themselves as innocent bystanders from the conventional "single experiment" practical laboratory to a path of practice and achievement in the scientific method.

Tailoring the Ag + Content within the Tunnels and on the Exposed Surfaces of α-MnO 2 Nanowires: Impact on Impedance and Electrochemistry

DOE PAGES

Zhang, Bingjie; Smith, Paul F.; Lee, Seung-Yong; ...

2016-12-01

Efficient conduction of both electrons and cations (e.g., Li +) has a profound effect on the current and capacity of lithium-based batteries. With this study, we focus on cathode effects, with the preparation of pure silver hollandite materials with variable silver ion content within (intra-tunnel) and on the surface of α-MnO 2 tunneled materials, followed by the measurement and analysis of impedance and electrochemistry data. Specifically, pure Ag xMn 8O 16-y materials with low (x = 1.13) and high (x = 1.54) intra-tunnel silver content are compared with Ag xMn 8O 16-y·aAg 2O (a = 0.25, 0.63, 1.43) composites preparedmore » via a new Ag 2O coating strategy. When the Ag 2O (a = 0, 0.25) content is low, the material with higher intra-tunnel silver (x = 1.53) content delivers up to ~5-fold higher capacity accounted for by a ~10-fold lower impedance than its lower intra-tunnel silver (x = 1.13) counterpart. In the presence of high Ag 2O content (a = 0.63, 1.43), both composites exhibit comparable impedance but the lower intra-tunnel silver (x = 1.13) composite delivers up to ~1.5-fold higher capacity than higher intra-tunnel silver composite, highlighting the key role of Li + transport under those conditions. Our results demonstrate material design strategies which can significantly increase electronic and ionic conductivities.« less

Tailoring the Ag + Content within the Tunnels and on the Exposed Surfaces of α-MnO 2 Nanowires: Impact on Impedance and Electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Bingjie; Smith, Paul F.; Lee, Seung-Yong

Efficient conduction of both electrons and cations (e.g., Li +) has a profound effect on the current and capacity of lithium-based batteries. With this study, we focus on cathode effects, with the preparation of pure silver hollandite materials with variable silver ion content within (intra-tunnel) and on the surface of α-MnO 2 tunneled materials, followed by the measurement and analysis of impedance and electrochemistry data. Specifically, pure Ag xMn 8O 16-y materials with low (x = 1.13) and high (x = 1.54) intra-tunnel silver content are compared with Ag xMn 8O 16-y·aAg 2O (a = 0.25, 0.63, 1.43) composites preparedmore » via a new Ag 2O coating strategy. When the Ag 2O (a = 0, 0.25) content is low, the material with higher intra-tunnel silver (x = 1.53) content delivers up to ~5-fold higher capacity accounted for by a ~10-fold lower impedance than its lower intra-tunnel silver (x = 1.13) counterpart. In the presence of high Ag 2O content (a = 0.63, 1.43), both composites exhibit comparable impedance but the lower intra-tunnel silver (x = 1.13) composite delivers up to ~1.5-fold higher capacity than higher intra-tunnel silver composite, highlighting the key role of Li + transport under those conditions. Our results demonstrate material design strategies which can significantly increase electronic and ionic conductivities.« less

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

DOE PAGES

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua; ...

2015-05-07

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

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

PubMed

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

2013-06-05

A graphene (GR) and multi-walled carbon nanotubes (MWCNT) hybrid was prepared and modified on a 1-hexylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE). Hemoglobin (Hb) was immobilized on GR-MWCNT/CILE surface with Nafion as the film forming material and the modified electrode was denoted as Nafion/Hb-GR-MWCNT/CILE. Spectroscopic results revealed that Hb molecules retained its native structure in the GR-MWCNT hybird. Electrochemical behaviors of Hb were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks obtained, which indicated that direct electron transfer of Hb was realized in the hybrid modified electrode. The result could be attributed to the synergistic effects of GR-MWCNT hybrid with enlarged surface area and improved conductivity through the formation of a three-dimensional network. Electrochemical parameters of the immobilized Hb on the electrode surface were further calculated with the results of the electron transfer number (n) as 1.03, the charge transfer coefficient (a) as 0.58 and the electron-transfer rate constant (ks) as 0.97 s(-1). The Hb modified electrode showed good electrocatalytic ability toward the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.05 to 38.0 mmol L(-1) with a detection limit of 0.0153 mmol L(-1) (3σ), H2O2 in the concentration range from 0.1 to 516.0 mmol L(-1) with a detection limit of 34.9 nmol/L (3σ) and NaNO2 in the concentration range from 0.5 to 650.0 mmol L(-1) with a detection limit of 0.282 μmol L(-1) (3σ). So the proposed electrode had the potential application in the third-generation electrochemical biosensors without mediator. Copyright © 2013 Elsevier B.V. All rights reserved.

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

PubMed

Repp, B H

1999-07-01

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

Le changement comme tradition dans la recherche et la formation a la recherche en biotechnologie et en peripherie Etude de cas en sciences de la sante, sciences naturelles et genie

NASA Astrophysics Data System (ADS)

Bourque, Claude Julie

Le champ de la recherche scientifique et de la formation a la recherche est traverse depuis quelques dizaines d'annees par plusieurs courants et discours associes au changement, mais peu de travaux empiriques permettent de comprendre ce qui change concretement. C'est la contribution originale de cette these au champ de l'education, plus specifiquement a l'etude sociologique de l'enseignement superieur ou sont concentrees les activites liees a la triade thematique du programme doctoral dans lequel elle a ete produite : recherche, formation et pratique. L'enquete-terrain a ete realisee en 2009 et 2010 aupres de 808 repondants affilies a 60 etablissements au Quebec et a produit un vaste materiau de nature mixte (donnees quantitatives et qualitatives). Un portrait de la nebuleuse biotechnologique qui touche les secteurs des sciences de la sante, des sciences naturelles et du genie a ete realise. Ce domaine concerne des dizaines de disciplines et se revele de nature transdisciplinaire, mais les pratiques n'y sont pas davantage marquees par le changement que celles d'autres domaines connexes. Les dynamiques sociales ont fait l'objet d'analyses comparatives dans quatre contextes: le choix des programmes, des objets et des methodes, le financement, la diffusion et la planification de la carriere. Les resultats indiquent que les echanges entre les agents traditionnellement situes au coeur des activites de recherche dominent ces dynamiques dans tous les contextes etudies. L'etude des representations au fondement des pratiques a revele l'existence de trois ecoles de pensee qui coexistent dans le champ scientifique: academique, pragmatique et economiste. Ces ecoles permettent de categoriser les agents en fonction des zones de fractures qui marquent leurs oppositions tout en identifiant ce qu'ils ont en commun. Les representations et les pratiques liees a la formation temoignent d'un habitus plutot homogene, alors que les contradictions semblent plus souvent ancrees dans des

Actes du colloque sur le bilinguisme, Universite de Neuchatel, 14/15 Septembre, 1981 (Proceedings of the Colloquium on Bilingualism, University of Neuchatel, September 14-15, 1981).

ERIC Educational Resources Information Center

TRANEL, 1982

1982-01-01

This issue contains proceedings of a colloquium on linguistics at the University of Neuchatel: (1) "Propositions epistemologiques pour une etude du bilinguisme (Epistemological Propositions for a Study of Bilingualism)," by B. Py; (2) "Comment on di ca? Prolegomenes a une etude de la composante semantique du langage des migrants (How Do You Say…

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

PubMed

Gholivand, Mohammad Bagher; Khodadadian, Mehdi

2014-03-15

Cholesterol oxidase (ChOx) and catalase (CAT) were co-immobilized on a graphene/ionic liquid-modified glassy carbon electrode (GR-IL/GCE) to develop a highly sensitive amperometric cholesterol biosensor. The H2O2 generated during the enzymatic reaction of ChOx with cholesterol could be reduced electrocatalytically by immobilized CAT to obtain a sensitive amperometric response to cholesterol. The direct electron transfer between enzymes and electrode surface was investigated by cyclic voltammetry. Both enzymes showed well-defined redox peaks with quasi-reversible behaviors. An excellent sensitivity of 4.163 mA mM(-1)cm(-2), a response time less than 6s, and a linear range of 0.25-215 μM (R(2)>0.99) have been observed for cholesterol determination using the proposed biosensor. The apparent Michaelis-Menten constant (KM(app)) was calculated to be 2.32 mM. The bienzymatic cholesterol biosensor showed good reproducibility (RSDs<5%) with minimal interference from the coexisting electroactive compounds such as ascorbic acid and uric acid. The CAT/ChOx/GR-IL/GCE showed excellent analytical performance for the determination of free cholesterol in human serum samples. © 2013 Elsevier B.V. All rights reserved.

Energetics of the Semiconductor-Electrolyte Interface.

ERIC Educational Resources Information Center

Turner, John A.

1983-01-01

The use of semiconductors as electrodes for electrochemistry requires an understanding of both solid-state physics and electrochemistry, since phenomena associated with both disciplines are seen in semiconductor/electrolyte systems. The interfacial energetics of these systems are discussed. (JN)

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

PubMed

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

2017-03-21

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.

HYDROGENATION OF OLEFINS USING PALLADIUM NANOPARTICLES PREPARED WITH PULSE ELECTROCHEMICAL DEPOSITION

EPA Science Inventory

Electrochemistry has been used to synthesize nano-structured materials. In this project, we have conducted the application of electrochemistry for the synthesis of nano-palladium catalysts that may have application in the area of green chemistry. The electrochemical technique use...

DNA Electrochemistry Shows DNMT1 Methyltransferase Hyperactivity in Colorectal Tumors.

PubMed

Furst, Ariel L; Barton, Jacqueline K

2015-07-23

DNMT1, the most abundant human methyltransferase, is responsible for translating the correct methylation pattern during DNA replication, and aberrant methylation by DNMT1 has been linked to tumorigenesis. We have developed a sensitive signal-on electrochemical assay for the measurement of DNMT1 activity in crude tissue lysates. We have further analyzed ten tumor sets and have found a direct correlation between DNMT1 hyperactivity and tumorous tissue. In the majority of samples analyzed, the tumorous tissue has significantly higher DNMT1 activity than the healthy adjacent tissue. No such correlation is observed in measurements of DNMT1 expression by qPCR, DNMT1 protein abundance by western blotting, or DNMT1 activity using a radiometric DNA labeling assay. DNMT1 hyperactivity can result from both protein overexpression and enzyme hyperactivity. DNMT1 activity measured electrochemically provides a direct measure of activity in cell lysates and, as a result, provides a sensitive and early indication of cancerous transformation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Proceedings from the DRG Seminar on Robotics in the Battlefield (31st) Held in Paris, France on 6-8 March 1991 (Acetes du 31ieme Seminaire sur la Robotique du Champ de Bataile)

DTIC Science & Technology

1992-06-01

8217Energie.4romnique) et GIAT-Industries (Groupern.ent Indusrriei dles Armements Terrestres ) ant 6t retenus ensemble par la DAT / SEFT (Direction des...Armements Terrestres , Sections d’Erudes et Fabrications des Tilicommunications ) pour une ’Etude de concepts de robots d-~ combat". Cette t6tude de dix...d’identification des amis utiusable par los ongins terrestres . *La t6l~opdration des armes utilisera des proc~dds sp~cifiques, no reprenant qu’en p

Optical Data Processing in Europe,

DTIC Science & Technology

1981-12-31

PROCESSING IN EUROPE4 _____________ 6PERFORMING ORG. REPORT NUMBER 7. AUTIKOR(eJ G . CONTRACT OR GRANT NUMBER(&) /7David/)Casasent 9. PERFORMING ORGANIZATION...Direction Des Recherches, Etudes et Techniques (DRET]). Present at this meeting were J. Graf, M. Petri and G . Marie of LEP as well as M. Constans and M...be useful in sonai , and processing studies. I visited Henri at Elf Aquitaine in Pau, Frarce. wt- w,-1. overall view of the company and a summary of

Investigation of α-MnO 2 Tunneled Structures as Model Cation Hosts for Energy Storage

DOE PAGES

Housel, Lisa M.; Wang, Lei; Abraham, Alyson; ...

2018-02-19

Future advances in energy storage systems rely on identification of appropriate target materials and deliberate synthesis of the target materials with control of their physiochemical properties in order to disentangling the contributions of distinct properties to the functional electrochemistry. Furthermore, this goal demands systematic inquiry using model materials that provide the opportunity for significant synthetic versatility and control. Ideally, a material family that enables direct manipulation of characteristics including composition, defects and crystallite size while remaining within the defined structural framework would be necessary. Accomplishing this through direct synthetic methods is desirable to minimize the complicating effects of secondary processing.

Investigation of α-MnO 2 Tunneled Structures as Model Cation Hosts for Energy Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Housel, Lisa M.; Wang, Lei; Abraham, Alyson

Future advances in energy storage systems rely on identification of appropriate target materials and deliberate synthesis of the target materials with control of their physiochemical properties in order to disentangling the contributions of distinct properties to the functional electrochemistry. Furthermore, this goal demands systematic inquiry using model materials that provide the opportunity for significant synthetic versatility and control. Ideally, a material family that enables direct manipulation of characteristics including composition, defects and crystallite size while remaining within the defined structural framework would be necessary. Accomplishing this through direct synthetic methods is desirable to minimize the complicating effects of secondary processing.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to 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

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

Who is more efficient: Teacher or pedagogical agents?

NASA Astrophysics Data System (ADS)

Lee, Tien Tien; Mustapha, Nur Hanani

2017-05-01

The purpose of the study is to investigate the impact of pedagogical agent's and teacher's role on students' understanding and motivation in the learning of Electrochemistry. Interactive Multimedia Module with Pedagogical Agents, EC Lab (IMMPA EC Lab) was used in this study. IMMPA EC Lab consists of five subunits in Electrochemistry topic. The research was a non-equivalent control group quasi experimental design involving two treatment groups and one control group. The first treatment group studied Electrochemistry with expert agent (Professor T) while the second treatment group studied Electrochemistry with learning companion agent (Lisa). On the other hand, the control group learned Electrochemistry with their Chemistry teacher using the material in the IMMPA EC Lab. The study was conducted at a secondary science school in the Pasir Puteh district involving 74 form four students. The instruments used in this research were the Electrochemistry achievement tests in the form of pre-test and post-test, IMMPA EC Lab and motivation questionnaire. ANCOVA results found that there was no significant difference among the three groups in post-test. On the other hand, One-way ANOVA test proved that there were significant differences for the post-motivation scores between the control group and the treatment groups. Post motivation mean scores for expert agent treatment group and learning companion treatment group surpassed the control group. The study focus on the impact of pedagogical agents with different roles on students' learning and motivation should be promoted. Various versions of pedagogical agents that fulfil the good characteristics should be designed to enhance students' learning and motivation.

Run-D.M.C.: A Mnemonic Aid for Explaining Mass Transfer in Electrochemical Systems

ERIC Educational Resources Information Center

Miles, Deon T.

2013-01-01

Electrochemistry is a significant area of analytical chemistry encompassing electrical measurements of chemical systems. The applications associated with electrochemistry appear in many aspects of everyday life: explaining how batteries work, how the human nervous system functions, and how metal corrosion occurs. The most common electrochemical…

High Surface Area Dendrite Nanoelectrodes for Electrochemistry

NASA Astrophysics Data System (ADS)

Nesbitt, Nathan; Glover, Jennifer; Goyal, Saurabh; Simidjiysky, Svetoslav; Naughton, Michael

2014-03-01

Solution-based electrodeposition of metal using a low ion concentration, surface passivation agents, and/or electrochemical crystal conditioning has allowed for the formation of high surface area metal electrodes, useful for Raman spectroscopy and electrochemical sensors. Additionally, high frequency electrical oscillations have been used to electrically connect co-planar electrodes, a process called directed electrochemical nanowire assembly (DENA). These approaches aim to control the crystal face that metal atoms in solution will nucleate onto, thus causing anisotropic growth of metal crystals. However, DENA has not been used to create high surface area electrodes, and no study has been conducted on the effect of micron-scale surface topography on the initial nucleation of metal crystals on the electrode surface. When DENA is used to create a high surface area electrode, such a texture has a strong impact on the subsequent topography of the three dimensional dendritic structures by limiting the areal density of crystals on the electrode surface. Such structures both demonstrate unique physics concerning the nucleation of metal dendrites, and offer a unique and highly facile fabrication method of high surface area electrodes, useful for chemical and biological sensing. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

From the Science Fair to the NASDAQ

ERIC Educational Resources Information Center

Kissinger, Peter T.

2007-01-01

Electrochemistry, which combines chemistry and electronics, is an exciting field and those who are in this field are very versatile scientists. Electrochemistry is a combination of true phenomena and an instrument to teach much about other fields and its technological advances touch many other fields as well.

Colloidal models. A bit of history.

PubMed

Lyklema, Johannes

2015-05-15

This paper offers an anthology on developments in colloid and interface science emphasizing themes that may be of direct or indirect interest to Interfaces Against Pollution. Topics include the determination of Avogadro's number, development in the insight into driving forces for double layer formation, colloid stability, thin films, and thermodynamic approaches in interfacial electrochemistry. Some personal reminiscences of key players in the field are included, partly to illustrate historical developments. Copyright © 2014 Elsevier Inc. All rights reserved.

Mise au point du rheometre a cisaillement annulaire pour l'etude de rheologie d'un mastic bitumineux avec verre incorpore =

NASA Astrophysics Data System (ADS)

El Mansouri, Souleimane

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

Propulsion and Energetics Panel Working Group 14 on Suitable Averaging Techniques in Non-Uniform Internal Flows

DTIC Science & Technology

1983-06-01

PANEL WORKING GROUP 14 on SUITABLE AVERAGING TECHNIQUES IN NON-UNIFORM INTERNAL FLOWS Edited by M.Pianko Office National d’Etudes et de...d’Etudes et de Recherches Aerospatiales Pratt and Whitney Government Products Division Rocketdyne Division of Rockwell International , Inc. Teledyne CAE...actions exerted by individual components on the gas flow must be known. These specific component effects are distributed internally within the

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

PubMed

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

2017-06-23

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

Grade 12 Students' Conceptual Understanding and Mental Models of Galvanic Cells before and after Learning by Using Small-Scale Experiments in Conjunction with a Model Kit

ERIC Educational Resources Information Center

Supasorn, Saksri

2015-01-01

This study aimed to develop the small-scale experiments involving electrochemistry and the galvanic cell model kit featuring the sub-microscopic level. The small-scale experiments in conjunction with the model kit were implemented based on the 5E inquiry learning approach to enhance students' conceptual understanding of electrochemistry. The…

Battery Relevant Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 : Contrasting Contributions from the Redox Chemistries of Ag + and Fe 3+

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Battery Relevant Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 : Contrasting Contributions from the Redox Chemistries of Ag + and Fe 3+

DOE PAGES

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

2016-10-12

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

Etude hydromecanique d'une fracture en cisaillement sous contrainte normale constante

NASA Astrophysics Data System (ADS)

Lamontagne, Eric

This research study deals with the effects of shear direction and injection flow rate on the flow directional anisotropy for a given normal stress. It presents experimental works on hydromechanical shear behaviour of a fracture under constant normal stress conditions that permits the characterisation of the intrinsic hydraulic transmissivity in relation with the directional anisotropy of the roughness morphology on the fracture surfaces. Tests were performed on mortar replicas of a natural fracture so that the fracture roughness and void space geometry were kept the same for each test. The experimental work program was performed through direct shear tests on the fracture replicas in four shear directions under four constant normal stress levels. The application of the normal stress was followed by several injections of fluid under constant flow rate. Then, for each defined shear displacement, several injections of fluid were done at different flow rate but under constant flow rate. The test results show that: (1) for the whole shear tests, the global intrinsic transmissivity is included within an enveloping zone of about one order of size. The transmissivity curves within the enveloping zone has a particularity to increase about two orders of size in the first millimetre of shear displacement and subsequently stabilised rapidly; (2) the highest dilatancy do not correspond necessarily with the highest intrinsic transmissivity so that, the behaviour of the global intrinsic transmissivity is not directly proportional to the fracture dilatancy during shear; (3) after the peak shear stress, the divergence is more marked between the global intrinsic transmissivity curves at various flow rate; (4) after peak shear strength and the beginning of asperity degradation, the gradual passage to residual friction shear behaviour causes a directional flow anisotropy and a reorientation of the flow chenalisation direction sub perpendicularly to the shear direction; (5) the

The Effects of Applied Stress and Sensitization on the Passive Film Stability of Al-Mg Alloys

DTIC Science & Technology

2013-06-01

and residual tensile and compressive stresses impact the passive layer film and the material’s electrochemistry. Sample plates of AA5083 were...electrochemistry. Sample plates of AA5083 were sensitized to different levels to promote the formation of intergranular β phase (Al3Mg2). The...41  A.  MATERIAL PROCESSING: FABRICATION AND APPLIED STRESSES OF TEST SAMPLES

Lithium Vanadium Oxide (Li 1.1V 3O 8) Coated with Amorphous Lithium Phosphorous Oxynitride (LiPON): Role of Material Morphology and Interfacial Structure on Resulting Electrochemistry

DOE PAGES

Zhang, Qing; Kercher, Andrew K.; Veith, Gabriel M.; ...

2017-05-16

In the present work, lithium vanadium oxide (Li 1.1V 3O 8) particles synthesized at two different temperatures were coated with an amorphous lithium phosphorous oxynitride (LiPON) film for the first time, and the effects of the LiPON coating on the electrochemistry of the Li 1.1V 3O 8 materials with different morphologies were systematically investigated by comparing uncoated Li 1.1V 3O 8 and Li 1.1V 3O 8 coated with LiPON of various thicknesses. Galvanostatic discharge-charge cycling revealed increased functional capacity for the LiPON-coated materials. Post-cycling electrochemical impedance spectroscopy showed that LiPON-coated Li 1.1V 3O 8 materials developed less interfacial resistance withmore » extended cycling, rationalized by vanadium migration into the LiPON coating seen by electron energy loss spectra. Post-mortem quantitative analysis of the anodes revealed more severe vanadium dissolution for the more irregularly shaped Li 1.1V 3O 8 materials with less LiPON coverage. Thus, this study highlights the specific benefits and limitations of LiPON coatings for stabilizing a moderate voltage Li 1.1V 3O 8 cathode material under extended cycling in liquid electrolyte, and describes a generally applicable approach for comprehensive characterization of a composite electroactive material which can be used to understand interfacial transport properties in other functional systems.« less

Lithium Vanadium Oxide (Li 1.1V 3O 8) Coated with Amorphous Lithium Phosphorous Oxynitride (LiPON): Role of Material Morphology and Interfacial Structure on Resulting Electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Qing; Kercher, Andrew K.; Veith, Gabriel M.

In the present work, lithium vanadium oxide (Li 1.1V 3O 8) particles synthesized at two different temperatures were coated with an amorphous lithium phosphorous oxynitride (LiPON) film for the first time, and the effects of the LiPON coating on the electrochemistry of the Li 1.1V 3O 8 materials with different morphologies were systematically investigated by comparing uncoated Li 1.1V 3O 8 and Li 1.1V 3O 8 coated with LiPON of various thicknesses. Galvanostatic discharge-charge cycling revealed increased functional capacity for the LiPON-coated materials. Post-cycling electrochemical impedance spectroscopy showed that LiPON-coated Li 1.1V 3O 8 materials developed less interfacial resistance withmore » extended cycling, rationalized by vanadium migration into the LiPON coating seen by electron energy loss spectra. Post-mortem quantitative analysis of the anodes revealed more severe vanadium dissolution for the more irregularly shaped Li 1.1V 3O 8 materials with less LiPON coverage. Thus, this study highlights the specific benefits and limitations of LiPON coatings for stabilizing a moderate voltage Li 1.1V 3O 8 cathode material under extended cycling in liquid electrolyte, and describes a generally applicable approach for comprehensive characterization of a composite electroactive material which can be used to understand interfacial transport properties in other functional systems.« less

Plates-formes de microscopie et fluorescence par resonance de plasmons de surface appliquees a l'imagerie cellulaire

NASA Astrophysics Data System (ADS)

Chabot, Vincent

L'elaboration de nouveaux medicaments repose sur les etudes pharmacologiques, dont le role est d'identifier de nouveaux composes actifs ou de nouvelles cibles pharmacologiques agissant entre autres au niveau cellulaire. Recemment, la detection basee sur la resonance des plasmons de surface (SPR) a ete appliquee a l'etude de reponses cellulaires. Cette methode de detection, permettant d'observer des variations d'indice de refraction associes a de faibles changements de masse a la surface d'un metal, a l'avantage de permettre l'etude d'une population de cellules vivantes en temps reel, sans necessiter l'introduction d'agents de marquage. Pour effectuer la detection au niveau de cellules individuelles, on peut employer la microscopie SPR, qui consiste a localiser spatialement la detection par un systeme d'imagerie. Cependant, la detection basee sur la SPR est une mesure sans marquage et les signaux mesures sont attribues a une reponse moyennee des differentes sources cellulaires. Afin de mieux comprendre et identifier les composantes cellulaires generant le signal mesure en SPR, il est pertinent de combiner la microscopie SPR avec une modalite complementaire, soit l'imagerie de fluorescence. C'est dans cette problematique que s'insere ce projet de these, consistant a concevoir deux plates-formes distinctes de microscopie SPR et de fluorescence optimisees pour l'etude cellulaire, de sorte a evaluer les possibilites d'integration de ces deux modalites en un seul systeme. Des substrats adaptes pour chaque plate-forme ont ete concus et realises. Ces substrats employaient une couche d'argent passivee par l'ajout d'une mince couche d'or. La stabilite et la biocompatibilite des substrats ont ete validees pour l'etude cellulaire. Deux configurations permettant d'ameliorer la sensibilite en sondant les cellules plus profondement ont ete evaluees, soit l'emploi de plasmons de surface a longue portee et de guides d'onde a gaine metallique. La sensibilite accrue de ces

Etude thermo-hydraulique de l'ecoulement du moderateur dans le reacteur CANDU-6

NASA Astrophysics Data System (ADS)

Mehdi Zadeh, Foad

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

New Organic-Inorganic Nanocomposite Materials for Energy Storage Applications

DTIC Science & Technology

1998-06-29

electrochemistry. The electrochemical experiments comprised charging (oxidation) and discharging (reduction) of the material, with the bulk of the...be expelled from the V205 interlayer region, leading to an evolution of the electrochemical response back to that of the original V205 material...composite material is characterized by uv-visible spectroelectrochemistry, x-ray diffraction, FTIR and electrochemistry. The electrochemical experiments

Successful Performance of Laboratory Investigations with Blood Glucose Meters Employing a Dynamic Electrochemistry-Based Correction Algorithm Is Dependent on Careful Sample Handling.

PubMed

Demircik, Filiz; Klonoff, David; Musholt, Petra B; Ramljak, Sanja; Pfützner, Andreas

2016-10-01

Devices employing electrochemistry-based correction algorithms (EBCAs) are optimized for patient use and require special handling procedures when tested in the laboratory. This study investigated the impact of sample handling on the results of an accuracy and hematocrit interference test performed with BG*Star, iBG*Star; OneTouch Verio Pro and Accu-Chek Aviva versus YSI Stat 2300. Venous heparinized whole blood was manipulated to contain three different blood glucose concentrations (64-74, 147-163, and 313-335 mg/dL) and three different hematocrit levels (30%, 45%, and 60%). Sample preparation was done by either a very EBCA-experienced laboratory testing team (A), a group experienced with other meters but not EBCAs (B), or a team inexperienced with meter testing (C). Team A ensured physiological pO 2 and specific sample handling requirements, whereas teams B and C did not consider pO 2 . Each sample was tested four times with each device. In a separate experiment, a different group similar to group B performed the experiment before (D1) and after (D2) appropriate sample handling training. Mean absolute deviation from YSI was calculated as a metrix for all groups and devices. Mean absolute relative difference was 4.3% with team A (B: 9.2%, C: 5.2%). Team B had much higher readings and team C produced 100% of "sample composition" errors with high hematocrit levels. In a separate experiment, group D showed a result similar to group B before the training and improved significantly when considering the sample handling requirements (D1: 9.4%, D2: 4.5%, P < 0.05). Laboratory performance testing of EBCA devices should only be performed by trained staff considering specific sample handling requirements. The results suggest that healthcare centers should evaluate EBCA-based devices with capillary blood from patients in accordance with the instructions for use to achieve reliable results.

Etude de la performance des radars hautes-frequences CODAR et WERA pour la mesure des courants marins en presence partielle de glace de mer

NASA Astrophysics Data System (ADS)

Kamli, Emna

Les radars hautes-frequences (RHF) mesurent les courants marins de surface avec une portee pouvant atteindre 200 kilometres et une resolution de l'ordre du kilometre. Cette etude a pour but de caracteriser la performance des RHF, en terme de couverture spatiale, pour la mesure des courants de surface en presence partielle de glace de mer. Pour ce faire, les mesures des courants de deux radars de type CODAR sur la rive sud de l'estuaire maritime du Saint-Laurent, et d'un radar de type WERA sur la rive nord, prises pendant l'hiver 2013, ont ete utilisees. Dans un premier temps, l'aire moyenne journaliere de la zone ou les courants sont mesures par chaque radar a ete comparee a l'energie des vagues de Bragg calculee a partir des donnees brutes d'acceleration fournies par une bouee mouillee dans la zone couverte par les radars. La couverture des CODARs est dependante de la densite d'energie de Bragg, alors que la couverture du WERA y est pratiquement insensible. Un modele de fetch appele GENER a ete force par la vitesse du vent predite par le modele GEM d'Environnement Canada pour estimer la hauteur significative ainsi que la periode modale des vagues. A partir de ces parametres, la densite d'energie des vagues de Bragg a ete evaluee pendant l'hiver a l'aide du spectre theorique de Bretschneider. Ces resultats permettent d'etablir la couverture normale de chaque radar en absence de glace de mer. La concentration de glace de mer, predite par le systeme canadien operationnel de prevision glace-ocean, a ete moyennee sur les differents fetchs du vent selon la direction moyenne journaliere des vagues predites par GENER. Dans un deuxieme temps, la relation entre le ratio des couvertures journalieres obtenues pendant l'hiver 2013 et des couvertures normales de chaque radar d'une part, et la concentration moyenne journaliere de glace de mer d'autre part, a ete etablie. Le ratio des couvertures decroit avec l'augmentation de la concentration de glace de mer pour les deux types

Reanalysis of European Flight Loads Data

DTIC Science & Technology

1994-05-01

DATA 6. Pulornig Ogaiation Cods 7. Authus) 8. Peronming Organization Report No. J. B. de Jonge, P.A. Hol and P.A. van Gelder NLR TP 93�L 9...containing data on aircraft operated by British Airways was obtained from the Office National d’etudes et de researches aerospatiales in France. A database...by British Airways. This data base was kept at Office National d’etudes et de recherches aerospatiales (ONERA) and was acquired from that institute

Use of X-Ray Fluorescence in a Laboratory for the Treatment of Uranium Ores; UTILISATION DE LA FLUORESCENCE DANS UN LABORATOIRE DE TRAITEMENTS DE MINERAIS D'URANIUM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guillet, H.

1960-01-01

A brief description is given of some aspects of the experience gained over a year during which x-ray fluorescence was used at the laberatory of the present Section Autonome d'Etudes, Recherches et Applications Chimiques of the Commissariat a l'Energie Atomique. A standard is tested daily to ensure reproducibility. The observations made during the months from Dec. 1958 to May 1959 are described. In acid leaching of uranium ores, the residues are analyzed by x-ray fluorescence directly in powder form. Fixation and elution of vanadium on ion-exchange resin were also studied. (auth)

Etude numerique et experimentale de la reponse vibro-acoustique des structures raidies a des excitations aeriennes et solidiennes

NASA Astrophysics Data System (ADS)

Mejdi, Abderrazak

compte. Les modeles developpes ont permis de conduire plusieurs etudes parametriques sur les proprietes vibro-acoustiques des structures d'avions facilitant ainsi la tache des concepteurs. Dans le cadre de cette these, un article a ete publie dans le Journal of Sound and Vibration et trois autres soumis, respectivement aux Journal of Acoustical Society of America, International Journal of Solid Mechanics et au Journal of Sound and Vibration Mots cles : structures raidies, composites, vibro-acoustique, perte par transmission.

The electrode/ionic liquid interface: electric double layer and metal electrodeposition.

PubMed

Su, Yu-Zhuan; Fu, Yong-Chun; Wei, Yi-Min; Yan, Jia-Wei; Mao, Bing-Wei

2010-09-10

The last decade has witnessed remarkable advances in interfacial electrochemistry in room-temperature ionic liquids. Although the wide electrochemical window of ionic liquids is of primary concern in this new type of solvent for electrochemistry, the unusual bulk and interfacial properties brought about by the intrinsic strong interactions in the ionic liquid system also substantially influence the structure and processes at electrode/ionic liquid interfaces. Theoretical modeling and experimental characterizations have been indispensable in reaching a microscopic understanding of electrode/ionic liquid interfaces and in elucidating the physics behind new phenomena in ionic liquids. This Minireview describes the status of some aspects of interfacial electrochemistry in ionic liquids. Emphasis is placed on high-resolution and molecular-level characterization by scanning tunneling microscopy and vibrational spectroscopies of interfacial structures, and the initial stage of metal electrodeposition with application in surface nanostructuring.

Porous Electrodes I: Numerical Simulation Using Random Network and Single Pore Models.

DTIC Science & Technology

1984-01-31

characteristic of Zn and ZnO ) and scaling them down to the magnitude of a unit pore size- approximately 10i in diameter. We define a characteristic...supported by the Office of Naval Research under contract N00014-81-K-0339. 11 - 15 - REFERENCES 1. R. de Levis in Advances in Electrochemistry and...P. 3. Hendra Dr. C. E. Mueller Department of Chemistry The Electrochemistry Branch University of Southampton Naval Surface Weapons Center

Directed polymers versus directed percolation

NASA Astrophysics Data System (ADS)

Halpin-Healy, Timothy

1998-10-01

Universality plays a central role within the rubric of modern statistical mechanics, wherein an insightful continuum formulation rises above irrelevant microscopic details, capturing essential scaling behaviors. Nevertheless, occasions do arise where the lattice or another discrete aspect can constitute a formidable legacy. Directed polymers in random media, along with its close sibling, directed percolation, provide an intriguing case in point. Indeed, the deep blood relation between these two models may have sabotaged past efforts to fully characterize the Kardar-Parisi-Zhang universality class, to which the directed polymer belongs.

Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy

NASA Astrophysics Data System (ADS)

Yuan, Yifei; Amine, Khalil; Lu, Jun; Shahbazian-Yassar, Reza

2017-08-01

An in-depth understanding of material behaviours under complex electrochemical environment is critical for the development of advanced materials for the next-generation rechargeable ion batteries. The dynamic conditions inside a working battery had not been intensively explored until the advent of various in situ characterization techniques. Real-time transmission electron microscopy of electrochemical reactions is one of the most significant breakthroughs poised to enable radical shift in our knowledge on how materials behave in the electrochemical environment. This review, therefore, summarizes the scientific discoveries enabled by in situ transmission electron microscopy, and specifically emphasizes the applicability of this technique to address the critical challenges in the rechargeable ion battery electrodes, electrolyte and their interfaces. New electrochemical systems such as lithium-oxygen, lithium-sulfur and sodium ion batteries are included, considering the rapidly increasing application of in situ transmission electron microscopy in these areas. A systematic comparison between lithium ion-based electrochemistry and sodium ion-based electrochemistry is also given in terms of their thermodynamic and kinetic differences. The effect of the electron beam on the validity of in situ observation is also covered. This review concludes by providing a renewed perspective for the future directions of in situ transmission electron microscopy in rechargeable ion batteries.

Electrocatalytic oxidation of hydrogen peroxide on a platinum electrode in the imitation of oxidative drug metabolism of lidocaine.

PubMed

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

2012-10-21

Electrochemistry in combination with mass spectrometry has shown promise as a versatile technique not only in the analytical assessment of oxidative drug metabolism, but also for small-scale synthesis of drug metabolites. However, electrochemistry is generally limited to reactions initiated by direct electron transfer. In the case of substituted-aromatic compounds, oxidation proceeds through a Wheland-type intermediate where resonance stabilization of the positive charge determines the regioselectivity of the anodic substitution reaction, and hence limits the extent of generating drug metabolites in comparison with in vivo oxygen insertion reactions. In this study, we show that the electrocatalytic oxidation of hydrogen peroxide on a platinum electrode generates reactive oxygen species, presumably surface-bound platinum-oxo species, which are capable of oxygen insertion reactions in analogy to oxo-ferryl radical cations in the active site of Cytochrome P450. Electrochemical oxidation of lidocaine at constant potential in the presence of hydrogen peroxide produces both 3- and 4-hydroxylidocaine, suggesting reaction via an arene oxide rather than a Wheland-type intermediate. No benzylic hydroxylation was observed, thus freely diffusing radicals do not appear to be present. The results of the present study extend the possibilities of electrochemical imitation of oxidative drug metabolism to oxygen insertion reactions.

Influencing the electronic interaction in diferrocenyl-1-phenyl-1H-pyrroles.

PubMed

Hildebrandt, Alexander; Lang, Heinrich

2011-11-28

Functionalised diferrocenyl-1-phenyl-1H-pyrroles were synthesised using Negishi C,C cross-coupling reactions. The influence of different substituents at the phenyl moiety on the electronic interaction was studied using electrochemistry (cyclic and square-wave voltammetry) and spectro-electrochemistry (in situ UV/Vis-NIR spectroscopy). The ferrocenyl moieties gave rise to two sequential, reversible redox processes in each of the diferrocenyl-1-phenyl-1H-pyrroles. The observed ΔE(1/2) values (ΔE(1/2) = difference between first and second oxidation) range between 420 and 480 mV. A linear relationship between the Hammett constants σ of the substituents and the separation of the redox potentials exists. The NIR measurements confirm electronic communication between the iron centers as intervalence charge transfer (IVCT) absorptions were observed in the corresponding mixed-valent monocationic species. All compounds were classified as class II systems according to Robin and Day (M. B. Robin and P. Day, Adv. Inorg. Chem., 1967, 10, 247-423). The oscillator strength of the charge transfer transition highly depends on the electron donating or electron withdrawing character of the phenyl substituents. This enables direct tuning of the intermetallic communication by simple modification of the molecule's functional group. Hence, this series of molecules may be regarded as model compounds for single molecule transistors.

Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy

PubMed Central

Yuan, Yifei; Amine, Khalil; Lu, Jun; Shahbazian-Yassar, Reza

2017-01-01

An in-depth understanding of material behaviours under complex electrochemical environment is critical for the development of advanced materials for the next-generation rechargeable ion batteries. The dynamic conditions inside a working battery had not been intensively explored until the advent of various in situ characterization techniques. Real-time transmission electron microscopy of electrochemical reactions is one of the most significant breakthroughs poised to enable radical shift in our knowledge on how materials behave in the electrochemical environment. This review, therefore, summarizes the scientific discoveries enabled by in situ transmission electron microscopy, and specifically emphasizes the applicability of this technique to address the critical challenges in the rechargeable ion battery electrodes, electrolyte and their interfaces. New electrochemical systems such as lithium–oxygen, lithium–sulfur and sodium ion batteries are included, considering the rapidly increasing application of in situ transmission electron microscopy in these areas. A systematic comparison between lithium ion-based electrochemistry and sodium ion-based electrochemistry is also given in terms of their thermodynamic and kinetic differences. The effect of the electron beam on the validity of in situ observation is also covered. This review concludes by providing a renewed perspective for the future directions of in situ transmission electron microscopy in rechargeable ion batteries.

A Fundamental Electrochemical Investigation of Bromoaluminate and Mixed Chloro-Bromoaluminate Room Temperature Molten Salt Systems

DTIC Science & Technology

1989-03-01

Non-Aqueous Bromide Research In the late 1950s, Alexander I. Popov and David H. Geske , published a series of papers dealing with the electrochemistry... Geske has also helped to illuminate the electrochemistry occurring in the Zinc-Bromine battery systems. In 1987 Adanuvor et al. studied the effects of the...oxidation waves present in the basic bromide melt system are due to some form of the bromide anion. While Popov and Geske 7 have attributed the first of

Expedient generation of patterned surface aldehydes by microfluidic oxidation for chemoselective immobilization of ligands and cells.

PubMed

Westcott, Nathan P; Pulsipher, Abigail; Lamb, Brian M; Yousaf, Muhammad N

2008-09-02

An expedient and inexpensive method to generate patterned aldehydes on self-assembled monolayers (SAMs) of alkanethiolates on gold with control of density for subsequent chemoselective immobilization from commercially available starting materials has been developed. Utilizing microfluidic cassettes, primary alcohol oxidation of tetra(ethylene glycol) undecane thiol and 11-mercapto-1-undecanol SAMs was performed directly on the surface generating patterned aldehyde groups with pyridinium chlorochromate. The precise density of surface aldehydes generated can be controlled and characterized by electrochemistry. For biological applications, fibroblast cells were seeded on patterned surfaces presenting biospecifc cell adhesive (Arg-Glyc-Asp) RGD peptides.

Glucose biosensing using glassy carbon electrode modified with polyhydroxy-C60, glucose oxidase and ionic-liquid.

PubMed

Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, BaoLin; Hong, Jun

2014-01-01

Direct electrochemistry of glucose oxidase (GOD) was achieved when an ionic liquid/GOD-Polyhydroxy-C60 functional membrane was confined on a glassy carbon electrode (GCE). The cyclic voltammograms (CVs) of the modified GCE showed a pair of redox peaks with a formal potential (E°') of - 329 ± 2 mV. The heterogeneous electron transfer constant (k(s)) was 1.43 s-1. The modified GCE response to glucose was linear in the range from 0.02 to 2.0 mM. The detection limit was 1 μM. The apparent Michaelis-Menten constant (K(m)(app)) was 1.45 mM.

Graphene Based Electrochemical Sensors and Biosensors: A Review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shao, Yuyan; Wang, Jun; Wu, Hong

2010-05-01

Graphene, emerging as a true 2-dimensional material, has received increasing attention due to its unique physicochemical properties (high surface area, excellent conductivity, high mechanical strength, and ease of functionalization and mass production). This article selectively reviews recent advances in graphene-based electrochemical sensors and biosensors. In particular, graphene for direct electrochemistry of enzyme, its electrocatalytic activity toward small biomolecules (hydrogen peroxide, NADH, dopamine, etc.), and graphene-based enzyme biosensors have been summarized in more detail; Graphene-based DNA sensing and environmental analysis have been discussed. Future perspectives in this rapidly developing field are also discussed.

78 FR 32533 - Proposed Collection of Information: Direct Deposit, Go Direct, and Direct Express Sign-Up Forms

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-30

... Deposit, Go Direct, and Direct Express Sign-Up Forms AGENCY: Bureau of the Fiscal Service, Fiscal Service... ``Direct Deposit Sign-Up Form'', Form 1200 ``Go Direct Sign-Up Form for Direct Deposit of Federal Benefit... information described below: Title: Direct Deposit Sign-Up Form, and Go Direct Sign-Up Form, and Direct...

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

NASA Astrophysics Data System (ADS)

Savard, Stephane

Les premieres etudes d'antennes a base de supraconducteurs a haute temperature critique emettant une impulsion electromagnetique dont le contenu en frequence se situe dans le domaine terahertz remontent a 1996. Une antenne supraconductrice est formee d'un micro-pont d'une couche mince supraconductrice sur lequel un courant continu est applique. Un faisceau laser dans le visible est focalise sur le micro-pont et place le supraconducteur dans un etat hors-equilibre ou des paires sont brisees. Grace a la relaxation des quasiparticules en surplus et eventuellement de la reformation des paires supraconductrices, nous pouvons etudier la nature de la supraconductivite. L'analyse de la cinetique temporelle du champ electromagnetique emis par une telle antenne terahertz supraconductrice s'est averee utile pour decrire qualitativement les caracteristiques de celle-ci en fonction des parametres d'operation tels que le courant applique, la temperature et la puissance d'excitation. La comprehension de l'etat hors-equilibre est la cle pour comprendre le fonctionnement des antennes terahertz supraconductrices a haute temperature critique. Dans le but de comprendre ultimement cet etat hors-equilibre, nous avions besoin d'une methode et d'un modele pour extraire de facon plus systematique les proprietes intrinseques du materiau qui compose l'antenne terahertz a partir des caracteristiques d'emission de celle-ci. Nous avons developpe une procedure pour calibrer le spectrometre dans le domaine temporel en utilisant des antennes terahertz de GaAs bombarde aux protons H+ comme emetteur et detecteur. Une fois le montage calibre, nous y avons insere une antenne emettrice dipolaire de YBa 2Cu3O7-delta . Un modele avec des fonctions exponentielles de montee et de descente du signal est utilise pour lisser le spectre du champ electromagnetique de l'antenne de YBa 2Cu3O7-delta, ce qui nous permet d'extraire les proprietes intrinseques de ce dernier. Pour confirmer la validite du modele

How to Develop Electrochemistry SETS-Based Interactive E-Book?

NASA Astrophysics Data System (ADS)

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

2017-09-01

This study aims to develop SETS-based interactive e-book teaching material through 4S TMD methode. The research methode in this study is the Development Research (RD) Richey and Klein that consists of design, phase, and evaluation. The design step was to analyze and plan the types of teaching materials instructional developed. There are 12 indicators from 3 standard competences that produced in selection step based new curriculum, the compatibility subject matter and indicators, and the relations between value and subject matter. Structuring steps yield concept map, macro structure, and multiple representation that were arranged to be first draft of teaching material that was used for develop the instruments for characterization step. Chatacterization test have been done to students in 12nd grades with 68 texts. Characterization results indicated that there were some texts included to difficult text. Difficult texts have been reduced with the ways back to qualitative steps and particulation. The second draft of teaching material was arranged based the results of didactic reduction of difficult texts. This draft was used for arranged interactive e-book. The characteristics of this SETS-based interactive e-book that developed were mention about the connection between science with environment, technology, and society. This interactive e-book consists of animation, task, and quizes that taken the interaction of students directly.

Enhanced Proton Conductivity of Sulfonated Hybrid Poly(arylene ether ketone) Membranes by Incorporating an Amino-Sulfo Bifunctionalized Metal-Organic Framework for Direct Methanol Fuel Cells.

PubMed

Ru, Chunyu; Li, Zhenhua; Zhao, Chengji; Duan, Yuting; Zhuang, Zhuang; Bu, Fanzhe; Na, Hui

2018-03-07

Novel side-chain-type sulfonated poly(arylene ether ketone) (SNF-PAEK) containing naphthalene and fluorine moieties on the main chain was prepared in this work, and a new amino-sulfo-bifunctionalized metal-organic framework (MNS, short for MIL-101-NH 2 -SO 3 H) was synthesized via a hydrothermal technology and postmodification. Then, MNS was incorporated into a SNF-PAEK matrix as an inorganic nanofiller to prepare a series of organic-inorganic hybrid membranes (MNS@SNF-PAEK-XX). The mechanical property, methanol resistance, electrochemistry, and other properties of MNS@SNF-PAEK-XX hybrid membranes were characterized in detail. We found that the mechanical strength and methanol resistances of these hybrid membranes were improved by the formation of an ionic cross-linking structure between -NH 2 of MNS and -SO 3 H on the side chain of SNF-PAEK. Particularly, the proton conductivity of these hybrid membranes increased obviously after the addition of MNS. MNS@SNF-PAEK-3% exhibited the proton conductivity of 0.192 S·cm -1 , which was much higher than those of the pristine membrane (0.145 S·cm -1 ) and recast Nafion (0.134 S·cm -1 ) at 80 °C. This result indicated that bifunctionalized MNS rearranged the microstructure of hybrid membranes, which could accelerate the transfer of protons. The hybrid membrane (MNS@SNF-PAEK-3%) showed a better direct methanol fuel cell performance with a higher peak power density of 125.7 mW/cm 2 at 80 °C and a higher open-circuit voltage (0.839 V) than the pristine membrane.

Development of Nanostructure Materials and Architecture for High Performance Li-rechargeable Batteries with Ultrafast Charge Rate

DTIC Science & Technology

2011-04-22

overcome these difficulties extensive work has been done. Surface coatings with ZnO , SiO2, and Bi2O3 have been proposed to enhance stability of electrodes...Liu, G. Q.; Wen, L.; Liu, Y. M. Journal of Solid State Electrochemistry 2010, 14, 2191. (23) Myung, S. T.; Komaba, S.; Kumagai, N.; Yashiro, H.; Chung...Y. R.; Shu, J.; Zhu, R. S. Journal of Solid State Electrochemistry 2009, 13, 913. (29) Aklalouch, M.; Amarilla, J. M.; Rojas, R. M.; Saadoune, I

Luminescent Photoelectrochemical Cells. 4. Electroluminescent Properties of Undoped and Tellurium-Doped Cadmium Sulfide Electrodes.

DTIC Science & Technology

1980-12-03

and/or Dist Special UnclassifiLed 26CURITY CLAIICATION OrY,.g PAWEWO 000 Ss~w" Introduction Anunderstanding of electrochemistry at semiconductor...studies: Electrolyte species capable of hole injection into the valence bands of n-type, semiconducting T102 SrTi’ 3 , CdS ,GaP ’ ZnO ,and GaAs...the denominator of (4) by using the total current as a measure of holes injected. If equations (1) and (2) truly describe the electrochemistry at the

ELECTROCHEMISTRY AND ON-CELL REFORMATION MODELING FOR SOLID OXIDE FUEL CELL STACKS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Recknagle, Kurtis P.; Jarboe, Daniel T.; Johnson, Kenneth I.

2007-01-16

ABSTRACT Providing adequate and efficient cooling schemes for solid-oxide-fuel-cell (SOFC) stacks continues to be a challenge coincident with the development of larger, more powerful stacks. The endothermic steam-methane reformation reaction can provide cooling and improved system efficiency when performed directly on the electrochemically active anode. Rapid kinetics of the endothermic reaction typically causes a localized temperature depression on the anode near the fuel inlet. It is desirable to extend the endothermic effect over more of the cell area and mitigate the associated differences in temperature on the cell to alleviate subsequent thermal stresses. In this study, modeling tools validated formore » the prediction of fuel use, on-cell methane reforming, and the distribution of temperature within SOFC stacks, are employed to provide direction for modifying the catalytic activity of anode materials to control the methane conversion rate. Improvements in thermal management that can be achieved through on-cell reforming is predicted and discussed. Two operating scenarios are considered: one in which the methane fuel is fully pre-reformed, and another in which a substantial percentage of the methane is reformed on-cell. For the latter, a range of catalytic activity is considered and the predicted thermal effects on the cell are presented. Simulations of the cell electrochemical and thermal performance with and without on-cell reforming, including structural analyses, show a substantial decrease in thermal stresses for an on-cell reforming case with slowed methane conversion.« less

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

PubMed

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

2015-01-01

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

The effects of printing orientation on the electrochemical behaviour of 3D printed acrylonitrile butadiene styrene (ABS)/carbon black electrodes.

PubMed

Bin Hamzah, Hairul Hisham; Keattch, Oliver; Covill, Derek; Patel, Bhavik Anil

2018-06-14

Additive manufacturing also known as 3D printing is being utilised in electrochemistry to reproducibly develop complex geometries with conductive properties. In this study, we explored if the electrochemical behavior of 3D printed acrylonitrile butadiene styrene (ABS)/carbon black electrodes was influenced by printing direction. The electrodes were printed in both horizontal and vertical directions. The horizsontal direction resulted in a smooth surface (HPSS electrode) and a comparatively rougher surface (HPRS electrode) surface. Electrodes were characterized using cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry. For various redox couples, the vertical printed (VP) electrode showed enhanced current response when compared the two electrode surfaces generated by horizontal print direction. No differences in the capacitive response was observed, indicating that the conductive surface area of all types of electrodes were identical. The VP electrode had reduced charge transfer resistance and uncompensated solution resistance when compared to the HPSS and HPRS electrodes. Overall, electrodes printed in a vertical direction provide enhanced electrochemical performance and our study indicates that print orientation is a key factor that can be used to enhance sensor performance.

Describing Directional Cell Migration with a Characteristic Directionality Time

PubMed Central

Loosley, Alex J.; O’Brien, Xian M.; Reichner, Jonathan S.; Tang, Jay X.

2015-01-01

Many cell types can bias their direction of locomotion by coupling to external cues. Characteristics such as how fast a cell migrates and the directedness of its migration path can be quantified to provide metrics that determine which biochemical and biomechanical factors affect directional cell migration, and by how much. To be useful, these metrics must be reproducible from one experimental setting to another. However, most are not reproducible because their numerical values depend on technical parameters like sampling interval and measurement error. To address the need for a reproducible metric, we analytically derive a metric called directionality time, the minimum observation time required to identify motion as directionally biased. We show that the corresponding fit function is applicable to a variety of ergodic, directionally biased motions. A motion is ergodic when the underlying dynamical properties such as speed or directional bias do not change over time. Measuring the directionality of nonergodic motion is less straightforward but we also show how this class of motion can be analyzed. Simulations are used to show the robustness of directionality time measurements and its decoupling from measurement errors. As a practical example, we demonstrate the measurement of directionality time, step-by-step, on noisy, nonergodic trajectories of chemotactic neutrophils. Because of its inherent generality, directionality time ought to be useful for characterizing a broad range of motions including intracellular transport, cell motility, and animal migration. PMID:25992908

Etude du processus de changement vecu par des familles ayant decide d'adopter volontairement des comportements d'attenuation des changements climatiques

NASA Astrophysics Data System (ADS)

Leger, Michel T.

recension des ecrits sur le changement de comportement en environnement. Nous explorons egalement la famille comme systeme fonctionnel de sorte a mieux comprendre ce contexte d'action environnementale qui est, a notre connaissance, peu etudie. Dans le deuxieme article, nous presentons nos resultats de recherche concernant les facteurs d'influence observes ainsi que les competences manifestees au cours du processus d'adoption de nouveaux comportements environnementaux dans trois familles. Enfin, le troisieme article presente les resultats du cas d'une quatrieme famille ou les membres vivent depuis longtemps des modes de vie ecologique. Dans le cadre d'une demarche d'analyse par theorisation ancree, l'etude de ce cas modele nous a permis d'approfondir les categories conceptuelles identifiees dans le deuxieme article de sorte a produire une modelisation de l'integration de comportements environnementaux dans le contexte de la famille. Les conclusions degagees grace a la recension des ecrits nous ont permis d'identifier les elements qui pourraient influencer l'adoption de comportements environnementaux dans des familles. La recension a aussi permis une meilleure comprehension des divers facteurs qui peuvent affecter l'adoption de comportements environnementaux et, enfin, elle a permis de mieux cerner le phenomene de changement de comportement dans le contexte de la famille consideree comme un systeme. En appliquant un processus d'analyse inductif, a partir de nos donnees qualitatives, les resultats de notre etude multi-cas nous ont indique que deux construits conceptuels semblent influencer l'adoption de comportements environnementaux en famille : 1) les valeurs biospheriques communes au sein de la famille et 2) les competences collectivement mises a profit collectivement durant l'essai de nouveaux comportements environnementaux. Notre modelisation du processus de changement dans des familles indique aussi qu'une dynamique familiale collaborative et la presence d'un groupe de

Structural Basis for Methylarginine-dependent Recognition of Aubergine by Tudor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, H.; Wang, J; Huang, Y

2010-01-01

Piwi proteins are modified by symmetric dimethylation of arginine (sDMA), and the methylarginine-dependent interaction with Tudor domain proteins is critical for their functions in germline development. Cocrystal structures of an extended Tudor domain (eTud) of Drosophila Tudor with methylated peptides of Aubergine, a Piwi family protein, reveal that sDMA is recognized by an asparagine-gated aromatic cage. Furthermore, the unexpected Tudor-SN/p100 fold of eTud is important for sensing the position of sDMA. The structural information provides mechanistic insights into sDMA-dependent Piwi-Tudor interaction, and the recognition of sDMA by Tudor domains in general.

Electrochemistry of Metal Surfaces

DTIC Science & Technology

1990-06-30

i) 3-pyridine carboxylic acid ( nicotinic acid, NA) binds to Pt surfaces through both the nitrogen atom and an oxygen atom of the carboxylate group...formed from aqueous electrolytes at Pt(1l1) electrode surfaces have been compared with the IR and Raman spectra of the unadsorbed compounds in order...vibrational absorptivities between EELS spectra of adsorbed species and IR and Raman spectra of the corresponding unadsorbed compounds (146). Of

Electrochemistry of Interhalogen Cathodes

DTIC Science & Technology

sources. Chlorine trifluoride , with a theoretical 2120 whr/lb in combination with lithium, is also known to support substantial current densities when... chlorine trifluoride as a power source cathode material. A half-cell study was made on dilute ClF3 solutions at 5C in 1 M NaF-HF by the cyclic

Electrochemistry in diabetes management.

PubMed

Heller, Adam; Feldman, Ben

2010-07-20

Diabetes devastates lives and burdens society. Hypoglycemic (low glucose) episodes cause blackouts, and severe ones are life-threatening. Periods of hyperglycemia (high glucose) cause circulatory disease, stroke, amputations, blindness, kidney failure and nerve degeneration. In this Account, we describe the founding of TheraSense, now a major part of Abbott Diabetes Care, and the development of two products that have improved the lives of people with diabetes. The first, a virtually painless microcoulometer (300 nL volume), the FreeStyle blood glucose monitoring system, was approved by the FDA and became available in 2000. In 2009, this system was used in more than one billion blood assays. The second, the enzyme-wiring based, subcutaneously-implanted FreeStyle Navigator continuous glucose monitoring system, was approved by the FDA and became available in the United States in 2008. The strips of the FreeStyle blood glucose monitoring system comprise a printed parallel plate coulometer, with a 50 microm gap between two facing printed electrodes, a carbon electrode and a Ag/AgCl electrode. The volume of blood between the facing plates is accurately controlled. The glucose is electrooxidized through catalysis by a glucose dehydrogenase (GDH) and an Os(2+/3+) redox mediator, which is reduced by the glucose-reduced enzyme and is electrooxidized on the carbon electrode. Initially the system used pyrroloquinoline quinone (PQQ)-dependent GDH but now uses flavin adenine dinucleotide (FAD)-dependent GDH. Because the facing electrodes are separated by such a small distance, shuttling of electrons by the redox couple could interfere with the coulometric assay. However, the Os(2+/3+) redox mediator is selected to have a substantially negative formal potential, between 0.0 and -0.2 V, versus that of the facing Ag/AgCl electrode. This makes the flow of a shuttling current between the two electrodes virtually impossible because the oxidized Os(3+) complex cannot be appreciably reduced at the more positively poised Ag/AgCl electrode. The FreeStyle Navigator continuous glucose monitoring system uses a subcutaneously implanted miniature plastic sensor connected to a transmitter to measure glycemia amperometrically and sends the information to a PDA-like device every minute. The sensor consists of a narrow (0.6 mm wide) plastic substrate on which carbon-working, Ag/AgCl reference, and carbon counter electrodes are printed in a stacked geometry. The active wired enzyme sensing layer covers only about 0.1 mm(2) of the working electrode and is overlaid by a flux-limiting membrane. It resides at about 5 mm depth in the subcutaneous adipose tissue and monitors glucose concentrations over the range 20-500 mg/dL. Its core component, a miniature, disposable, amperometric glucose sensor, has an electrooxidation catalyst made from a crosslinked adduct of glucose oxidase (GOx) and a GOx wiring redox hydrogel containing a polymer-bound Os(2+/3+) complex. Because of the selectivity of the catalyst for glucose, very little current flows in the absence of glucose. That feature, either alone or in combination with other features of the sensor, facilitates the one-point calibration of the system. The sensor is implanted subcutaneously and replaced by the patient after 5 days use with minimal pain. The wearer does not feel its presence under the skin.

ELECTROCHEMISTRY OF FUSED SALTS.

DTIC Science & Technology

Chronopotentiometric and electrolysis data indicate the formation of Li2O.2V2O4V2O5 during the first reduction process of V2O5 in molten LiCl-KCl...The results were obtained with a pyrographite cathode. Also discussed is the spectra of CO(2+) and Ni(2+) in molten and solid sulfate media. (Author)

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.

Direct measurements on imaging riometer antenna array beam directivities

NASA Astrophysics Data System (ADS)

Wilson, A.; Nel, J. J.; Mathews, M. J.; Stoker, P. H.

2001-01-01

Spatial structures in enhanced ionization of the ionosphere are observed by absorption of cosmic radio waves. These structures are resolved by using theoretically derived imaging riometer antenna array directivities. These directivities are calculated from beam phasing of 64 crossed dipole elements of the 38.2-MHz antenna array at SANAE IV, Antarctica. In order to ensure that these derived directivities are representative of the actual viewing directions of the 64-beams, a radio transmitter was flown by helicopter across the antenna array. In this paper variations in the receiver signal strengths, recorded when flying across beam-viewing directions, are compared with the spatial and angular-dependent profiles of expected receiver output responses, derived theoretically from the directivities of the antenna array. A Global Positioning System (GPS) device on board the helicopter was used for positional recording. The derived and recorded profiles did coincide occasionally, but at other instances relative displacements and differences in magnitude of responses were observed. These displacements and differences could be attributed to degradation in position fixes imposed deliberately by selective availability on the GPS system. Excellent coincidence for a number of beam crossings proved that the viewing directions are accurate in all the beam directions, since the multi-dimensional Butler matrix produces 64 simultaneous beams.

Covalent dimers of 1,3-diphenylisobenzofuran for singlet fission: synthesis and electrochemistry.

PubMed

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

2015-01-02

The synthesis of covalent dimers in which two 1,3-diphenylisobenzofuran units are connected through one phenyl substituent on each is reported. In three of the dimers, the subunits are linked directly, and in three others, they are linked via an alkane chain. A seventh new compound in which two 1,3-diphenylisobenzofuran units share a phenyl substituent is also described. These materials are needed for investigations of the singlet fission process, which promises to increase the efficiency of solar cells. The electrochemical oxidation and reduction of the monomer, two previously known dimers, and the seven new compounds have been examined, and reversible redox potentials have been compared with results obtained from density functional theory. Although the overall agreement is satisfactory, some discrepancies are noted and discussed.

Dark matter directional detection: comparison of the track direction determination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Couturier, C.; Zopounidis, J.P.; Sauzet, N.

Several directional techniques have been proposed for a directional detection of Dark matter, among others anisotropic crystal detectors, nuclear emulsion plates, and low-pressure gaseous TPCs. The key point is to get access to the initial direction of the nucleus recoiling due to the elastic scattering by a WIMP. In this article, we aim at estimating, for each method, how the information of the recoil track initial direction is preserved in different detector materials. We use the SRIM simulation code to emulate the motion of the first recoiling nucleus in each material. We propose the use of a new observable, Dmore » , to quantify the preservation of the initial direction of the recoiling nucleus in the detector. We show that in an emulsion mix and an anisotropic crystal, the initial direction is lost very early, while in a typical TPC gas mix, the direction is well preserved.« less

Verification of the directivity index and other measures of directivity in predicting directional benefit

NASA Astrophysics Data System (ADS)

Dittberner, Andrew; Bentler, Ruth

2005-09-01

The relationship between various directivity measures and subject performance with directional microphone hearing aids was determined. Test devices included first- and second-order directional microphones. Recordings of sentences and noise (Hearing in Noise Test, HINT) were made through each test device in simple, complex, and anisotropic background noise conditions. Twenty-six subjects, with normal hearing, were administered the HINT test recordings, and directional benefit was computed. These measures were correlated to theoretical, free-field, and KEMAR DI values, as well as front-to-back ratios, in situ SNRs, and a newly proposed Db-SNR, wherein a predictive value of the SNR improvement is calculated as a function of the noise source incidence. The different predictive scores showed high correlation to the measured directional benefit scores in the complex (diffuse-like) background noise condition (r=0.89-0.97, p<0.05) but not across all background noise conditions (r=0.45-0.97, p<0.05). The Db-SNR approach and the in situ SNR measures provided excellent prediction of subject performance in all background noise conditions (0.85-0.97, p<0.05) None of the predictive measures could account for the effects of reverberation on the speech signal (r=0.35-0.40, p<0.05).

Co-clustering directed graphs to discover asymmetries and directional communities

PubMed Central

Rohe, Karl; Qin, Tai; Yu, Bin

2016-01-01

In directed graphs, relationships are asymmetric and these asymmetries contain essential structural information about the graph. Directed relationships lead to a new type of clustering that is not feasible in undirected graphs. We propose a spectral co-clustering algorithm called di-sim for asymmetry discovery and directional clustering. A Stochastic co-Blockmodel is introduced to show favorable properties of di-sim. To account for the sparse and highly heterogeneous nature of directed networks, di-sim uses the regularized graph Laplacian and projects the rows of the eigenvector matrix onto the sphere. A nodewise asymmetry score and di-sim are used to analyze the clustering asymmetries in the networks of Enron emails, political blogs, and the Caenorhabditis elegans chemical connectome. In each example, a subset of nodes have clustering asymmetries; these nodes send edges to one cluster, but receive edges from another cluster. Such nodes yield insightful information (e.g., communication bottlenecks) about directed networks, but are missed if the analysis ignores edge direction. PMID:27791058

Co-clustering directed graphs to discover asymmetries and directional communities.

PubMed

Rohe, Karl; Qin, Tai; Yu, Bin

2016-10-21

In directed graphs, relationships are asymmetric and these asymmetries contain essential structural information about the graph. Directed relationships lead to a new type of clustering that is not feasible in undirected graphs. We propose a spectral co-clustering algorithm called di-sim for asymmetry discovery and directional clustering. A Stochastic co-Blockmodel is introduced to show favorable properties of di-sim To account for the sparse and highly heterogeneous nature of directed networks, di-sim uses the regularized graph Laplacian and projects the rows of the eigenvector matrix onto the sphere. A nodewise asymmetry score and di-sim are used to analyze the clustering asymmetries in the networks of Enron emails, political blogs, and the Caenorhabditis elegans chemical connectome. In each example, a subset of nodes have clustering asymmetries; these nodes send edges to one cluster, but receive edges from another cluster. Such nodes yield insightful information (e.g., communication bottlenecks) about directed networks, but are missed if the analysis ignores edge direction.

Contribution a l'etude et au developpement de nouvelles poudres de fonte

NASA Astrophysics Data System (ADS)

Boisvert, Mathieu

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

Electrografting of alkyl films at low driving force by diverting the reactivity of aryl radicals derived from diazonium salts.

PubMed

Hetemi, Dardan; Kanoufi, Frédéric; Combellas, Catherine; Pinson, Jean; Podvorica, Fetah I

2014-11-25

Alkyl and partial perfluoroalkyl groups are strongly attached to carbon surfaces through (i) the abstraction of the iodine atom from an iodoalkane by the sterically hindered 2,6-dimethylphenyl radical and (ii) the reaction of the ensuing alkyl radical with the carbon surface. Since the 2,6-dimethylphenyl radical is obtained at -0.25 V/Ag/AgCl by reducing the corresponding diazonium salt, the electrografting reaction is facilitated by ∼1.7 V by comparison with the direct electrografting of the iodo compounds. Layers of various thicknesses, including monolayers, are obtained by controlling the time duration of the electrolysis. The grafted films are characterized by electrochemistry, IR, XPS, ellipsometry, and water contact angles.

Electrocatalyzed O2 response of myoglobin immobilized on multi-walled carbon nanotube forest electrodes.

PubMed

Pacios, M; del Valle, M; Bartroli, J; Esplandiu, M J

2009-10-01

Direct electrochemistry and activity of myoglobin (Mb) immobilized on carbon nanotube (CNT) forest electrodes were investigated by probing mainly its electrocatalytical response towards oxygen. The protein was anchored on the CNT electrodes through carbodiimide coupling, which was shown to provide long term stability. The electrochemical response was monitored as a function of oxygen concentration and pH. Conformational changes together with the consequent loss of oxygen affinity were recorded at low pH, which delimits the operative range of the Mb/CNT electrodes for sensing purposes. In general, it can be concluded that CNT forests constitute suitable platforms for Mb attachment without compromising the protein bioactivity and by keeping at the same time the direct electron exchange with the heme core. All these characteristics confer to the protein modified CNT system promising properties for the implementation of (bio)sensor devices with impact in the clinical and environmental field.

Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase*

PubMed Central

Wu, Sheng-Yi; Rothery, Richard A.; Weiner, Joel H.

2015-01-01

We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser719, NarG-His1163, and NarG-His1184); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His1092 and NarG-His1098). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of −88 and −36 mV, respectively). Ala variants of His1092 and His1098 also elicit large ΔEm values of −143 and −101 mV, respectively. An Arg variant of His1092 elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. PMID:26297003

Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase.

PubMed

Wu, Sheng-Yi; Rothery, Richard A; Weiner, Joel H

2015-10-09

We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser(719), NarG-His(1163), and NarG-His(1184)); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His(1092) and NarG-His(1098)). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of -88 and -36 mV, respectively). Ala variants of His(1092) and His(1098) also elicit large ΔEm values of -143 and -101 mV, respectively. An Arg variant of His(1092) elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Investigation of Voronoi diagram based direction choices using uni- and bi-directional trajectory data

NASA Astrophysics Data System (ADS)

Xiao, Yao; Chraibi, Mohcine; Qu, Yunchao; Tordeux, Antoine; Gao, Ziyou

2018-05-01

In a crowd, individuals make different motion choices such as "moving to destination," "following another pedestrian," and "making a detour." For the sake of convenience, the three direction choices are respectively called destination direction, following direction, and detour direction in this paper. Here, it is found that the featured direction choices could be inspired by the shape characteristics of the Voronoi diagram. To be specific, in the Voronoi cell of a pedestrian, the direction to a Voronoi node is regarded as a potential "detour" direction and the direction perpendicular to a Voronoi link is regarded as a potential "following" direction. A pedestrian generally owns several alternative Voronoi nodes and Voronoi links in a Voronoi cell, and the optimal detour and following direction are determined by considering related factors such as deviation. Plus the destination direction which is directly pointing to the destination, the three basic direction choices are defined in a Voronoi cell. In order to evaluate the Voronoi diagram based basic directions, the empirical trajectory data in both uni- and bi-directional flow experiments are extracted. A time series method considering the step frequency is used to reduce the original trajectories' swaying phenomena which might disturb the recognition of actual forward direction. The deviations between the empirical velocity direction and the basic directions are investigated, and each velocity direction is classified into a basic direction or regarded as an inexplicable direction according to the deviations. The analysis results show that each basic direction could be a potential direction choice for a pedestrian. The combination of the three basic directions could cover most empirical velocity direction choices in both uni- and bi-directional flow experiments.

Electrochemical oxidation coupled with liquid chromatography and mass spectrometry to study the oxidative stability of active pharmaceutical ingredients in solution: A comparison of off-line and on-line approaches.

PubMed

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

2016-11-30

Stability studies of pharmaceutical drug products and pharmaceutical active substances are important to research and development in order to fully understand and maintain product quality and safety throughout its shelf-life. Oxidative forced degradation studies are among the different types of stability studies performed by the pharmaceutical industry in order to understand the intrinsic stability of drug molecules. We have been comparing the use of electrochemistry as an alternative oxidative forced degradation method to traditional forced degradation and accelerated stability studies. Using the electrochemical degradation approach the substrate oxidation takes place in a commercially available electrochemical cell and the effluent of the cell can be either a) directly infused into the mass spectrometer or b) injected in a chromatographic column for separation of the different products formed prior to the mass spectrometry analysis. To enable the study of large numbers of different experimental conditions and molecules we developed a new dual pump automated electrochemical screening platform. This system used a HPLC pump and autosampler to load and wash the electrochemical cell and deliver the oxidized sample plug to a second injection loop. This system enabled the automatic sequential analyses of large numbers of different solutions under varied experimental conditions without need for operator intervention during the run sequence. Here we describe the system and evaluate its performance using a test molecule with well characterized stability and compare results to those obtained using an off-line electrochemistry approach. Copyright © 2016 Elsevier B.V. All rights reserved.

Electrochemistry with double electrical layers in frictional interaction metal-polymer tribolink

NASA Astrophysics Data System (ADS)

Volchenko, N. A.; Krasin, P. S.; Volchenko, D. A.; Voznyi, A. V.

2018-03-01

The materials of the article illustrate the estimation of the energy loading of a metal friction element in a “metal-electrolyte-polymer” friction pair while forming various types of double electrical layers with the release of its thermal stabilization state. The rapidity of the processes of oxidation and reduction of the working surfaces of friction pairs during their electrothermomechanical frictional interaction leaves an imprint on all other additional processes that subsequently lead to the thermostabilizing and steady state of the metal friction element. Depending on the type of a brake device, the metal friction element has a different metal consumption and the temperature range varies. In addition, it is shown that the materials of the friction pair play an important role in the formation of electric tribosystems, namely: chemical elements that make up the materials, their valence, and the predominant type of intrinsic conductivity, as well as the sign of the electric charge of the friction pair elements that determines the laws of triboelectricity. Thus, an in-depth approach to the evaluation of the thermal stabilization state of a metal element in a “metal-electrolyte” friction pair is shown due to double electric layers that promote the emergence of current densities of different directions.

Frontal transcranial direct current stimulation (tDCS) abolishes list-method directed forgetting.

PubMed

Silas, Jonathan; Brandt, Karen R

2016-03-11

It is a point of controversy as to whether directed forgetting effects are a result of active inhibition or a change of context initiated by the instruction to forget. In this study we test the causal role of active inhibition in directed forgetting. By applying cathodal transcranial direct current stimulation (tDCS) over the right prefrontal cortex we suppressed cortical activity commonly associated with inhibitory control. Participants who underwent real brain stimulation before completing the directed forgetting paradigm showed no directed forgetting effects. Conversely, those who underwent sham brain stimulation demonstrated classical directed forgetting effects. We argue that these findings suggest that inhibition is the primary mechanism that results in directed forgetting costs and benefits. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Etude exploratoire des conceptions de la circulation sanguine aupres d'eleves de l'ordre collegial

NASA Astrophysics Data System (ADS)

Robitaille, Jean-Marc

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

Direction Finding Using an Antenna with Direction Dependent Impulse Response

NASA Technical Reports Server (NTRS)

Foltz, Heinrich; Kegege, Obadiah

2016-01-01

Wideband antennas may be designed to have an impulse response that is direction dependent, not only in amplitude but also in waveform shape. This property can be used to perform direction finding using a single fixed antenna, without the need for an array or antenna rotation. In this paper direction finding is demonstrated using a simple candelabra-shaped monopole operating in the 1-3 GHz range. The method requires a known transmitted pulse shape and high signal-to-noise ratio, and is not as accurate or robust as conventional methods. However, it can add direction finding capability to a wideband communication system without the addition of any hardware.

RESEARCH ACTIVITIES IN THE FIELD OF MATERIALS SCIENCE.

DTIC Science & Technology

MAGNETIC RESONANCE, COMPLEX COMPOUNDS, CRYSTAL STRUCTURE, ELECTROCHEMISTRY, CHEMILUMINESCENCE, PHOTOCHEMICAL REACTIONS, PHOSPHORUS HETEROCYCLIC COMPOUNDS...RADIATION CHEMISTRY, POLYMERS, ROCK, SUPERCONDUCTORS, POSITRONS , DAMAGE, RADIATION EFFECTS, HALIDES

Enhanced direct electrochemistry of glucose oxidase and biosensing for glucose via synergy effect of graphene and CdS nanocrystals.

PubMed

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

2011-01-15

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

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

PubMed

Hong, Jun; Wang, Wei; Huang, Kun; Yang, Wei-Yun; Zhao, Ying-Xue; Xiao, Bao-Lin; Gao, Yun-Fei; Moosavi-Movahedi, Zainab; Ghourchian, Hedayatollah; Moosavi-Movahedi, Ali Akbar

2012-01-01

A nano-cluster with highly efficient peroxide activity was constructed based on nafion (NF) and cytochrome c (Cyt c). UV-Vis spectrometry and transmission electron microscopy (TEM) methods were utilized for characterization of the nano-structured enzyme or artificial peroxidase (AP). The nano-cluster was composed of a Chain-Ball structure, with an average ball size of about 40 nm. The Michaelis-Menten (K(m)) and catalytic rate (k(cat)) constants of the AP were determined to be 2.5 ± 0.4 µM and 0.069 ± 0.001 s(-1), respectively, in 50 mM PBS at pH 7.0. The catalytic efficiency of the AP was evaluated to be 0.028 ± 0.005 µM(-1) s(-1), which was 39 ± 5% as efficient as the native horseradish peroxidase (HRP). The AP was also immobilized on a functional multi-wall carbon nanotube (MWNCTs)-gold colloid nanoparticles (AuNPs) nano-complex modified glassy carbon (GC) electrode. The cyclic voltammetry of AP on the nano complex modified GC electrode showed a pair of well-defined redox peaks with a formal potential (E°') of -45 ± 2 mV (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer rate constant (k(s)) was evaluated to be 0.65 s(-1). The surface concentration of electroactive AP on GC electrode (Γ) was 7 × 10(-10) mol cm(-2). The apparent Michaelis-Menten constant (K(m)(app)) was 0.23 nM.

Harmonizing Self-Directed and Teacher-Directed Approaches to Learning.

ERIC Educational Resources Information Center

Bell, Deanne F.; Bell, Durward L.

1983-01-01

A combination of self-directed learning and teacher-directed learning provides a rich and flexible learning experience and accommodates various teaching styles. The key to a successful mixture is the appropriate use of criterion-referencing and normative-referencing for learner evaluation. (JOW)

Directional output distance functions: endogenous directions based on exogenous normalization constraints

USDA-ARS?s Scientific Manuscript database

In this paper we develop a model for computing directional output distance functions with endogenously determined direction vectors. We show how this model is related to the slacks-based directional distance function introduced by Fare and Grosskopf and show how to use the slacks-based function to e...

Are recent empirical directivity models sufficient in capturing near-fault directivity effect?

NASA Astrophysics Data System (ADS)

Chen, Yen-Shin; Cotton, Fabrice; Pagani, Marco; Weatherill, Graeme; Reshi, Owais; Mai, Martin

2017-04-01

It has been widely observed that the ground motion variability in the near field can be significantly higher than that commonly reported in published GMPEs, and this has been suggested to be a consequence of directivity. To capture the spatial variation in ground motion amplitude and frequency caused by the near-fault directivity effect, several models for engineering applications have been developed using empirical or, more recently, the combination of empirical and simulation data. Many research works have indicated that the large velocity pulses mainly observed in the near-field are primarily related to slip heterogeneity (i.e., asperities), suggesting that the slip heterogeneity is a more dominant controlling factor than the rupture velocity or source rise time function. The first generation of broadband directivity models for application in ground motion prediction do not account for heterogeneity of slip and rupture speed. With the increased availability of strong motion recordings (e.g., NGA-West 2 database) in the near-fault region, the directivity models moved from broadband to narrowband models to include the magnitude dependence of the period of the rupture directivity pulses, wherein the pulses are believed to be closely related to the heterogeneity of slip distribution. After decades of directivity models development, does the latest generation of models - i.e. the one including narrowband directivity models - better capture the near-fault directivity effects, particularly in presence of strong slip heterogeneity? To address this question, a set of simulated motions for an earthquake rupture scenario, with various kinematic slip models and hypocenter locations, are used as a basis for a comparison with the directivity models proposed by the NGA-West 2 project for application with ground motion prediction equations incorporating a narrowband directivity model. The aim of this research is to gain better insights on the accuracy of narrowband directivity

Future direction of direct writing

NASA Astrophysics Data System (ADS)

Kim, Nam-Soo; Han, Kenneth N.

2010-11-01

Direct write technology using special inks consisting of finely dispersed metal nanoparticles in liquid is receiving an undivided attention in recent years for its wide range of applicability in modern electronic industry. The application of this technology covers radio frequency identification-tag (RFID-tag), flexible-electronics, organic light emitting diodes (OLED) display, e-paper, antenna, bumpers used in flip-chip, underfilling, frit, miniresistance applications and biological uses, artificial dental applications and many more. In this paper, the authors have reviewed various direct write technologies on the market and discussed their advantages and shortfalls. Emphasis has given on microdispensing deposition write (MDDW), maskless mesoscale materials deposition (M3D), and ink-jet technologies. All of these technologies allow printing various patterns without employing a mask or a resist with an enhanced speed with the aid of computer. MDDW and M3D are capable of drawing patterns in three-dimension and MDDW, in particular, is capable of writing nanoinks with high viscosity. However, it is still far away for direct write to be fully implemented in the commercial arena. One of the hurdles to overcome is in manufacturing conductive inks which are chemically and physically stable, capable of drawing patterns with acceptable conductivity, and also capable of drawing patterns with acceptable adhesiveness with the substrates. The authors have briefly discussed problems involved in manufacturing nanometal inks to be used in various writing devices. There are numerous factors to be considered in manufacturing such inks. They are reducing agents, concentrations, oxidation, compact ability allowing good conductivity, and stability in suspension.

A comparison of consumer-directed and agency-directed personal assistance services programmes.

PubMed

Hagglund, Kristofer; Clark, Mary; Farmer, Janet; Sherman, Ashley

2004-05-06

To compare a consumer-directed personal assistance services (PAS) programme with an agency-directed PAS programme. A convenience sample was used for this cross-sectional study with one data collection point. Outcomes were compared for consumer-directed and agency-directed PAS. Hierarchical regressions were also used to determine the predictors of outcomes across PAS programmes. In-home interviews were conducted by a trained data collector from April 2000 to December 2001. Participants in the consumer-directed programme reported more choices over PAS and satisfaction with PAS. Self-reported outcomes were primarily predicted by the following variables: service arrangement, type of provider, importance of directing PAS, health status, number of personal assistants used in past 12 months, sufficient PAS hours received, and social support. Consumer-directed PAS enhances outcomes for many persons with disabilities. Self-reported outcomes are affected by many factors that could be addressed in PAS programme development.

Official portrait of STS-65 backup Payload Specialist Jean-Jacques Favier

NASA Image and Video Library

1993-09-30

Official portrait of STS-65 International Microgravity Laboratory 2 (IML-2) backup Payload Specialist Jean-Jacques Favier. Favier is a member of the Centre National D'Etudes Spatiales (CNES), the French space agency.

Directing 101.

ERIC Educational Resources Information Center

Pintoff, Ernest

Providing an introduction to anyone considering directing as a field of study or career, this book takes a broad look at the process of directing and encourages students and professionals alike to look outside of the movie industry for inspiration. Chapters in the book discuss selecting and acquiring material; budgeting and financing; casting and…

Directed Energy Weapons

DTIC Science & Technology

2007-12-01

future business . In defense systems, the key to future business is the existence of funded programs. Military commanders understand the lethality and...directed energp capabilities that can provide visibiliy into the likey futur business case for sustaining directed energy industry capabilities...the USD (I) staff to be afocalpointfor advocating improvement in all dimensions of directed energy intelligence. - The Director, Defense Inteligence

Driving Directions

Science.gov Websites

close X Directions to the Automotive Research Center North Campus, University of Michigan W.E. Lay directions and a map of visitor parking lots. From I-94: Take Exit 180B onto US-23 North. Take Exit 41 to parking permit is displayed prominently. North Campus parking map close X

Emotional consequences of collective action participation: differentiating self-directed and outgroup-directed emotions.

PubMed

Becker, Julia C; Tausch, Nicole; Wagner, Ulrich

2011-12-01

The present research examines the emotional and behavioral consequences of collective action participation. It demonstrates that "positive" and "negative" emotions can be experienced simultaneously as a result of collective action participation, yet it is important to distinguish outgroup-directed from self-directed emotions. Results of two experiments (N = 71 and N = 101) that manipulated participation in collective action illustrate that whereas collective action participants experience more outgroup-directed anger and contempt, they feel more self-directed positive affect. Furthermore, collective action participation predicted willingness to engage in moderate and radical collective actions in the future. These relations were mediated by outgroup-directed, but not by self-directed, emotions, suggesting that outgroup-directed rather than self-directed emotions play a crucial role in the maintenance of protest behavior. Theoretical and practical implications of these findings are discussed.

Directional radiation detectors

DOEpatents

Dowell, Jonathan L.

2017-09-12

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

The Electrochemistry of Organophosphorus Compounds.

DTIC Science & Technology

1988-01-20

of hydrogen on the electrode surface. Mechanistkc views are further developed with the addition of water resulting in the formation of...the exclusive vlide product. Furthermore, carbonvl compounds were added to the electrolyses to react with the electrochemically-generated ylides via...the Wittig reaction. The resulting olefins were found to catalytically isomerize from the Z isomer to the E isomer upon reduction. The role of water

Principles for system level electrochemistry

NASA Technical Reports Server (NTRS)

Thaller, L. H.

1986-01-01

The higher power and higher voltage levels anticipated for future space missions have required a careful review of the techniques currently in use to preclude battery problems that are related to the dispersion characteristics of the individual cells. Not only are the out-of-balance problems accentuated in these larger systems, but the thermal management considerations also require a greater degree of accurate design. Newer concepts which employ active cooling techniques are being developed which permit higher rates of discharge and tighter packing densities for the electrochemical components. This paper will put forward six semi-independent principles relating to battery systems. These principles will progressively address cell, battery and finally system related aspects of large electrochemical storage systems.

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…

Electrochemistry and Storage Panel Report

NASA Technical Reports Server (NTRS)

Stedman, J. K.; Halpert, G.

1984-01-01

Design and performance requirements for electrochemical power storage systems are discussed and some of the approaches towards satisfying these constraints are described. Geosynchronous and low Earth orbit applications, radar type load constraints, and high voltage systems requirements are addressed. In addition, flywheel energy storage is discussed.

Electrochemistry at Very Small Electrodes.

DTIC Science & Technology

1985-09-01

Reticulated Vitreous Carbon ", N. Sleazynaki, J. G. Osterycung end -’ M. Carter, October, 1983. *15’ * "Increased Electrochemical Window in Ambient...and R.A. Osteryoung, J. Electrochem. Soc., 130, 1965 (1983). 15. "Arrays of Very Small Electrodes Based on Reticulated Vitreous Carbon ", N. Sleszynski

Directed network modules

NASA Astrophysics Data System (ADS)

Palla, Gergely; Farkas, Illés J.; Pollner, Péter; Derényi, Imre; Vicsek, Tamás

2007-06-01

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

Green synthesis of carbon quantum dots embedded onto titanium dioxide nanowires for enhancing photocurrent

NASA Astrophysics Data System (ADS)

Yen, Yin-Cheng; Lin, Chia-Chi; Chen, Ping-Yu; Ko, Wen-Yin; Tien, Tzu-Rung; Lin, Kuan-Jiuh

2017-05-01

The green synthesis of nanowired photocatalyst composed of carbon quantum dots-titanium hybrid-semiconductors, CQDs/TiO2, are reported. Where graphite-based CQDs with a size less than 5 nm are directly synthesized in pure water electrolyte by a one-step electrochemistry approach and subsequently electrodeposited onto as-prepared TiO2 nanowires through a voltage-driven reduction process. Electron paramagnetic resonance studies show that the CQDs can generate singlet oxygen and/or oxygen radicals to decompose the kinetic H2O2 intermediate species upon UV light illumination. With the effect of peroxidase-like CQDs, photocurrent density of CQDs/TiO2 is remarkably enhanced by a 6.4 factor when compared with that of as-prepared TiO2.

Polymeric micelle assembly for the smart synthesis of mesoporous platinum nanospheres with tunable pore sizes.

PubMed

Li, Yunqi; Bastakoti, Bishnu Prasad; Malgras, Victor; Li, Cuiling; Tang, Jing; Kim, Jung Ho; Yamauchi, Yusuke

2015-09-14

A facile method for the fabrication of well-dispersed mesoporous Pt nanospheres involves the use of a polymeric micelle assembly. A core-shell-corona type triblock copolymer [poly(styrene-b-2-vinylpyridine-b-ethylene oxide), PS-b-P2VP-b-PEO] is employed as the pore-directing agent. Negatively charged PtCl4 (2-) ions preferably interact with the protonated P2VP(+) blocks while the free PEO chains prevent the aggregation of the Pt nanospheres. The size of the mesopores can be finely tuned by varying the length of the PS chain. Furthermore, it is demonstrated that the metallic mesoporous nanospheres thus obtained are promising candidates for applications in electrochemistry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct seeding

Treesearch

Richard M. Godman; G. A. Mattson

1992-01-01

At present, direct seeding of hardwoods in the Lake States is more of a supplemental than a primary means of artificial regeneration. Direct seeding may be used to augment a poor seed crop or increase the proportion of a preferred species. In the future, it will no doubt play a bigger role-in anticipation of this we need to collect and store the amounts of seed needed...

Variable mode bi-directional and uni-directional computer communication system

DOEpatents

Cornett, Frank N.; Jenkins, Philip N.; Bowman, Terrance L.; Placek, Joseph M.; Thorson, Gregory M.

2004-12-14

A variable communication systems comprising a plurality of transceivers and a control circuit connected to the transceivers to configure the transceivers to operate in a bi-directional mode and a uni-directional mode at different times using different transfer methods to transfer data.

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

HBA1c: clinical and biological agreement for standardization of assay methods. Report by the experts of ALFEDIAM (Association de Langue Française pour lEtude du Diabète et des Maladies Métabolique) and SFBC (Société Française de Biologie Clinique).

PubMed

Gillery, P; Bordas-Fonfrède, M; Chapelle, J P; Drouin, P; Hue, G; Lévy-Marchal, C; Périer, C; Sélam, J L; Slama, G; Thivolet, C; Vialettes, B

1999-09-01

Glycohaemoglobin, and particularly haemoglobin A1c(HbA1c), assays have been used for many years to retrospectively evaluate the glycaemic control of diabetic patients. Cut-off values have been established for deciding treatment modifications. The techniques used in the laboratories however exhibit varying quality, and all of them are not yet standardized. The consequence is an under-utilization of this test, especially in non-hospital practice. In this context, working groups of Société Française de Biologie Clinique (SFBC), Association de Langue Française pour l'Etude du Diabète et des Maladies Métaboliques (ALFEDIAM) and Société Française d'Endocrinologie (SFE) have met together, in order to analyze the national status, and to propose practical recommendations for implementing a standardization process on the basis of international experiences. It is recommended to exclusively express results as HbA1c percentage, using methods standardized and certified by comparison to reference methods such as those using Diabetes Control and Complications Trial (DCCT) values. Simultaneously, contacts have been established with manufacturers, and the realisation of periodic quality control surveys was encouraged.

Directivity of singers

NASA Astrophysics Data System (ADS)

Jers, Harald

2005-09-01

Studies of acoustical balance between singers within a choir by means of room acoustical measurements have shown that the directional sound propagation of the source is important. For this reason the directivity of female and male singers for different vowels has been measured in this investigation. Measurements of a pilot study and some first measurements in 1998 have been supplemented with new measurements and an enhanced setup. A special measurement setup with reference and recording microphones was used to collect the directivity data. A resolution of 10 deg for azimuth and elevation angle was obtained. The results will be shown in 3D spherical plots with frequency adjustments in semitones from 80 to 8000 Hz. The measurements are compared to an artificial singer's directivity, and the influence of a sheet music binder in front of a singer will be shown. The results give information on the directivity of singers and are relevant for the prediction of self-to-other-ratios that result from placement and formation aspects within a choir.

Science Update: Inorganic Chemistry.

ERIC Educational Resources Information Center

Rawls, Rebecca

1981-01-01

Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)

Short Wave Direction Finders

DTIC Science & Technology

1960-05-23

or designing direction finders. In CIApter 1, written by candidate of technical sciences, lec- turer O.V.Belavin, are considered direction finding...direction finding methods. In the design of radio direction finders with long base, qustioons arise of the advantageous choice of an antenna system, of the...dieeoticfindors, and reoommadat4ons on the design of radio direetion finders from the point of view of reduting the asaratu errors. og-’eae re~.o dkitctlon

Overhead Projector Demonstrations.

ERIC Educational Resources Information Center

Kolb, Doris, Ed.

1987-01-01

Describes several chemistry demonstrations that use an overhead projector. Some of the demonstrations deal with electrochemistry, and another deals with the reactions of nonvolatile immiscible liquid in water. (TW)

GRC-2013-C-04615

NASA Image and Video Library

2010-01-16

Advanced Exploration Systems (AES) Modular Power Systems for Space Exploration (AMPS); electrochemistry, AMPS, will infuse and demonstrate batteries, fuel cells, and other power modules for exploration ground system demonstrations

GRC-2013-C-04614

NASA Image and Video Library

2010-01-16

Advanced Exploration Systems (AES) Modular Power Systems for Space Exploration (AMPS); electrochemistry, AMPS, will infuse and demonstrate batteries, fuel cells, and other power modules for exploration ground system demonstrations

GRC-2013-C-04608

NASA Image and Video Library

2010-01-16

Advanced Exploration Systems (AES) Modular Power Systems for Space Exploration (AMPS); electrochemistry, AMPS, will infuse and demonstrate batteries, fuel cells, and other power modules for exploration ground system demonstrations

GRC-2013-C-04609

NASA Image and Video Library

2010-01-16

Advanced Exploration Systems (AES) Modular Power Systems for Space Exploration (AMPS); electrochemistry, AMPS, will infuse and demonstrate batteries, fuel cells, and other power modules for exploration ground system demonstrations

Estimating directional epistasis

PubMed Central

Le Rouzic, Arnaud

2014-01-01

Epistasis, i.e., the fact that gene effects depend on the genetic background, is a direct consequence of the complexity of genetic architectures. Despite this, most of the models used in evolutionary and quantitative genetics pay scant attention to genetic interactions. For instance, the traditional decomposition of genetic effects models epistasis as noise around the evolutionarily-relevant additive effects. Such an approach is only valid if it is assumed that there is no general pattern among interactions—a highly speculative scenario. Systematic interactions generate directional epistasis, which has major evolutionary consequences. In spite of its importance, directional epistasis is rarely measured or reported by quantitative geneticists, not only because its relevance is generally ignored, but also due to the lack of simple, operational, and accessible methods for its estimation. This paper describes conceptual and statistical tools that can be used to estimate directional epistasis from various kinds of data, including QTL mapping results, phenotype measurements in mutants, and artificial selection responses. As an illustration, I measured directional epistasis from a real-life example. I then discuss the interpretation of the estimates, showing how they can be used to draw meaningful biological inferences. PMID:25071828

The Influence of Directional Associations on Directed Forgetting and Interference

ERIC Educational Resources Information Center

Sahakyan, Lili; Goodmon, Leilani B.

2007-01-01

Two experiments examined how cross-list directional associations influenced list-method directed forgetting and the degree of interference observed on each list. Each List 1 item had a (a) bidirectionally related item on List 2 (chip ?? potato), (b) forward association with an item on List 2 (chip ? wood), (c) backward association from an item on…

Direction-Dependence Analysis: A Confirmatory Approach for Testing Directional Theories

ERIC Educational Resources Information Center

Wiedermann, Wolfgang; von Eye, Alexander

2015-01-01

The concept of direction dependence has attracted growing attention due to its potential to help decide which of two competing linear regression models (X ? Y or Y ? X) is more likely to reflect the correct causal flow. Several tests have been proposed to evaluate hypotheses compatible with direction dependence. In this issue, Thoemmes (2015)…

Introduction to Atomic Structure: Demonstrations and Labs.

ERIC Educational Resources Information Center

Ciparick, Joseph D.

1988-01-01

Demonstrates a variety of electrical phenomena to help explain atomic structure. Topics include: establishing electrical properties, electrochemistry, and electrostatic charges. Recommends demonstration equipment needed and an explanation of each. (MVL)

An Electrochemical Experiment Using an Optically Transparent Thin Layer Electrode

ERIC Educational Resources Information Center

DeAngelis, Thomas P.; Heineman, William R.

1976-01-01

Describes a unified experiment in which an optically transparent thin layer electrode is used to illustrate the techniques of thin layer electrochemistry, cyclic voltammetry, controlled potential coulometry, and spectroelectrochemistry. (MLH)

Directive sources in acoustic discrete-time domain simulations based on directivity diagrams.

PubMed

Escolano, José; López, José J; Pueo, Basilio

2007-06-01

Discrete-time domain methods provide a simple and flexible way to solve initial boundary value problems. With regard to the sources in such methods, only monopoles or dipoles can be considered. However, in many problems such as room acoustics, the radiation of realistic sources is directional-dependent and their directivity patterns have a clear influence on the total sound field. In this letter, a method to synthesize the directivity of sources is proposed, especially in cases where the knowledge is only based on discrete values of the directivity diagram. Some examples have been carried out in order to show the behavior and accuracy of the proposed method.

Etude de la Generation des Ultrasons Par Laser dans un Materiau Composite

NASA Astrophysics Data System (ADS)

Dubois, Marc

Laser generation of ultrasound is not a new subject. Many authors have proposed mathematical models of the thermoelastic process of generation of acoustic waves. However, none of those models, up to now, could take simultaneously the effects of the thermal conduction, the optical penetration, the anisotropy of the material and any time and surface profiles of the laser excitation into account. The model presented in this work takes all these parameters into consideration in the case of an infinite orthotropic plate. The mathematical approach used allows to obtain an analytical solution of the mechanical displacement field in the Laplace and two-dimensional (2-D) Fourier spaces. Numerical inverse Laplace and 2-D Fourier transformations bring the mechanical displacement field back into the normal spaces. The use of direct numerical transformations enables to consider almost any time and spatial distributions of the generation laser beam. The acoustic displacements calculated by this model have been compared to experimental displacements measured with a wide band optical detection system. The features of this system allow the quantitative measurement of the parallel and normal displacements to the surface of the sample. Hence, the calculated normal and parallel displacements have been compared to those experimentally measured at various locations on aluminum, glass and polymer samples. In all cases, the agreement between the calculated and experimentally measured displacements was good. The semi-analytical model having proved its validity, it has been used, in addition to a completely analytical one-dimensional model, to study the effects of the optical penetration and the laser pulse duration on the longitudinal acoustic wave generated. This study has established that a short enough laser pulse and a large irradiation with regard to the sample thickness allows to determine quantitatively, from the full width at half maximum of the acoustic pulse, the optical

Protecting me from my Directive: Ensuring Appropriate Safeguards for Advance Directives in Dementia.

PubMed

Auckland, Cressida

2018-02-01

With one in six people over 80 now suffering from dementia, advance directives provide an important means of empowerment. Upholding directives in the context of dementia, however, raises extra challenges, given the potential for the directive to conflict with an assessment of what is in the person's current best interests. Given the profound harm that tying a person with dementia to their previous wishes can do, it is essential that we have sufficient safeguards in place to ensure that we only uphold such directives where we can be sure they are truly autonomous and are intended to apply to the situation at hand-safeguards which are at present, severely lacking. This article will consider various mechanisms by which safeguards can be built into the legal regime to ensure that the original decision is autonomous, including making it mandatory for the person to undergo a consultation with a healthcare professional, which would involve a contemporaneous capacity assessment. Clinicians must also be confident that the directive applies to the situation at hand. Introducing formalities, including a standardised (though not mandatory) proforma, may help to enhance specificity about when the directive is triggered, and to what treatments it relates, to enable clinicians to better assess the directive's applicability. A national registry for advance directives might also be beneficial. It will be argued that health care professionals will have to play a much greater role in the drafting and registering of advance directives, if we are to feel comfortable in upholding them.

Wedge filter imaging spectrometer

NASA Astrophysics Data System (ADS)

Bernardi, Pernelle; Bonafous, M.; Motisi, M.; Reess, J.-M.; Tanrin, J.; Laubier, D.

2017-11-01

LESIA (Laboratoire d'Etudes Spatiales et d'Instrumentation en Astrophysique, Observatoire de Paris-Meudon) has an extensive experience in visible and infrared imaging spectrometry with several instruments onboard planetary space missions (MarsExpress/OMEGA, VenusExpress/VIRTIS, Rosetta/VIRTIS).

Directional Scanning as a Function of Stimulus Characteristics, Reading Habits, and Directional Set

ERIC Educational Resources Information Center

Nachshon, Israel; And Others

1977-01-01

"32 English readers and 32 Hebrew readers were shown stimuli with directional characteristics (English and Hebrew letters) and stimuli with no directional characteristics (arrays of different circles, bars, colors, and geometric figures) for scanning. The results showed that, while directional stimulus characteristics affected the direction…

Rubber friction directional asymmetry

NASA Astrophysics Data System (ADS)

Tiwari, A.; Dorogin, L.; Steenwyk, B.; Warhadpande, A.; Motamedi, M.; Fortunato, G.; Ciaravola, V.; Persson, B. N. J.

2016-12-01

In rubber friction studies it is usually assumed that the friction force does not depend on the sliding direction, unless the substrate has anisotropic properties, like a steel surface grinded in one direction. Here we will present experimental results for rubber friction, where we observe a strong asymmetry between forward and backward sliding, where forward and backward refer to the run-in direction of the rubber block. The observed effect could be very important in tire applications, where directional properties of the rubber friction could be induced during braking.

Direct current transformer

NASA Technical Reports Server (NTRS)

Khanna, S. M.; Urban, E. W. (Inventor)

1979-01-01

A direct current transformer in which the primary consists of an elongated strip of superconductive material, across the ends of which is direct current potential is described. Parallel and closely spaced to the primary is positioned a transformer secondary consisting of a thin strip of magnetoresistive material.

Self-Directed Workplace Learning.

ERIC Educational Resources Information Center

1998

This document contains four papers from a symposium on self-directed workplace learning. "Self-Directed Work Teams: Implementation and Performance" (Marcel van der Klink, Hilde ter Horst) discusses the results of a study examining the implementation and effects of self-directed work teams in a land register office and the role of the…

Directing the Lithium-Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries.

PubMed

Lee, Chang-Wook; Pang, Quan; Ha, Seungbum; Cheng, Lei; Han, Sang-Don; Zavadil, Kevin R; Gallagher, Kevin G; Nazar, Linda F; Balasubramanian, Mahalingam

2017-06-28

The lithium-sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium-sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium-sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium-sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. This discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation-dissolution chemistries, lithium-sulfur and beyond.

High Performance Liquid Chromatography Experiments to Undergraduate Laboratories

ERIC Educational Resources Information Center

Kissinger, Peter T.; And Others

1977-01-01

Reviews the principles of liquid chromatography with electrochemical detection (LCEC), an analytical technique that incorporates the advantages of both liquids chromatography and electrochemistry. Also suggests laboratory experiments using this technique. (MLH)

Tactile pavement for guiding walking direction: An assessment of heading direction and gait stability.

PubMed

Pluijter, Nanda; de Wit, Lieke P W; Bruijn, Sjoerd M; Plaisier, Myrthe A

2015-10-01

For maintaining heading direction while walking we heavily rely on vision. Therefore, walking in the absence of vision or with visual attention directed elsewhere potentially leads to dangerous situations. Here we investigated whether tactile information from the feet can be used as a (partial) substitute for vision in maintaining a stable heading direction. If so, participants should be better able to keep a constant heading direction on tactile pavement that indicates directionality than on regular flat pavement. However, such a pavement may also be destabilizing. Thus we asked participants to walk straight ahead on regular pavement, and on tactile pavement (tiles with ridges along the walking direction) while varying the amount of vision. We assessed the effects of the type of pavement as well as the amount of vision on the variability of the heading direction as well as gait stability. Both of these measures were calculated from accelerations and angular velocities recorded from a smartphone attached to the participants trunk. Results showed that on tactile pavement participants had a less variations in their heading direction than on regular pavement. The drawback, however, was that the tactile pavement used in this study decreased gait stability. In sum, tactile pavement can be used as a partial substitute for vision in maintaining heading direction, but it can also decrease gait stability. Future work should focus on designing tactile pavement that does provided directional clues, but is less destabilizing. Copyright © 2015 Elsevier B.V. All rights reserved.

Modelling directional solidification

NASA Technical Reports Server (NTRS)

Wilcox, William R.

1991-01-01

The long range goal of this program is to develop an improved understanding of phenomena of importance to directional solidification and to enable explanation and prediction of differences in behavior between solidification on Earth and in space. Current emphasis is on determining the influence of perturbations on directional solidification.

Reconfigurable Optical Directed-Logic Circuits

DTIC Science & Technology

2015-11-20

AFRL-AFOSR-VA-TR-2016-0053 Reconfigurable Optical Directed-Logic Circuits Jacob Robinson WILLIAM MARSH RICE UNIV HOUSTON TX Final Report 11/20/2015...2015 Reconfigurable Optical Directed-Logic Circuits FA9550-12-1-0261 FA9550-12-1-0261 Robinson, Jacob Rice University 6100 Main Street Houston...Optical Directed-Logic Circuits Jacob T. Robinson and Qianfan Xu Rice University 1. Motivation for Directed-Logic Circuits Directed-logic is

Multimode Directional Coupler

NASA Technical Reports Server (NTRS)

Simons, Rainee N. (Inventor); Wintucky, Edwin G. (Inventor)

2016-01-01

A multimode directional coupler is provided. In some embodiments, the multimode directional coupler is configured to receive a primary signal and a secondary signal at a first port of a primary waveguide. The primary signal is configured to propagate through the primary waveguide and be outputted at a second port of the primary waveguide. The multimode directional coupler also includes a secondary waveguide configured to couple the secondary signal from the primary waveguide with no coupling of the primary signal into the secondary waveguide. The secondary signal is configured to propagate through the secondary waveguide and be outputted from a port of the secondary waveguide.

Modelling Directional Solidification

NASA Technical Reports Server (NTRS)

Wilcox, William R.; Regel, Liya L.; Zhou, Jian; Yuan, Weijun

1992-01-01

The long range goal of this program has been to develop an improved understanding of phenomena of importance to directional solidification, in order to enable explanation and prediction of differences in behavior between solidification on Earth and in space. Current emphasis is on determining the influence of perturbations on directional solidification.

DIRECTIONAL ANTENNA

DOEpatents

Bittner, B.J.

1958-05-20

A high-frequency directional antenna of the 360 d scaring type is described. The antenna has for its desirable features the reduction in both size and complexity of the mechanism for rotating the antenna through its scanning movement. These advantages result from the rotation of only the driven element, the reflector remaining stationary. The particular antenna structure comprises a refiector formed by a plurality of metallic slats arranged in the configuration of an annular cage having the shape of a zone of revolution. The slats are parallel to each other and are disposed at an angle of 45 d to the axis of the cage. A directional radiator is disposed inside the cage at an angle of 45 d to the axis of the cage in the same direction as the reflecting slats which it faces. As the radiator is rotated, the electromagnetic wave is reflected from the slats facing the radiator and thereafter passes through the cage on the opposite side, since these slats are not parallel with the E vector of the wave.

The Shape of Direct Quotation

ERIC Educational Resources Information Center

Weber, Rose-Marie

2008-01-01

Direct quotation can be a source of meaning in storybook texts for beginning readers. The author of this article sketches the linguistic complexity of direct quotation and offers instructional strategies. Three aspects of direct quotation are examined: the cluster of print features and syntactic characteristics that direct quotation involves, the…

Synthesis of graphene supported Li2SiO3 as a high performance anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yang, Shuai; Wang, Qiufen; Miao, Juan; Zhang, Jingyang; Zhang, Dafeng; Chen, Yumei; Yang, Hong

2018-06-01

The Li2SiO3-graphene composite is successfully synthesized through an easy hydrothermal method. The structures and morphologies of the produced samples are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectrum, Brunauer-Emmett-Teller formalism, scanning electron microscope, transmission electron microscope, and electrochemistry methods. The result shows a well crystalline of the Li2SiO3-GE composite. The existence of graphene doesn't change the crystalline of Li2SiO3. In addition, the Li2SiO3 compound with an average diameter of 20 nm can be seen on the surface of graphene with uniform distribution. After the composite with graphene, the composite displays large surface area which ensures the well electrochemistry of the composite. Finally, the Li2SiO3-graphene composite delivers a high initial capacity of 878.3 mAh g-1 at 1C as well as a high recovery capacity of 400 mAh g-1 after 200 cycles. When charged and discharged at high rate, the Li2SiO3-doping graphene composite still exhibits a high specific capacity of 748.3 mAh g-1 (at 2C, and 576 mAh g-1 at 5C) and well cycling performance. The well synthesized composite possesses well structure and well electrochemistry performance.

Nanoscale heterogeneity at the aqueous electrolyte-electrode interface

NASA Astrophysics Data System (ADS)

Limmer, David T.; Willard, Adam P.

2015-01-01

Using molecular dynamics simulations, we reveal emergent properties of hydrated electrode interfaces that while molecular in origin are integral to the behavior of the system across long times scales and large length scales. Specifically, we describe the impact of a disordered and slowly evolving adsorbed layer of water on the molecular structure and dynamics of the electrolyte solution adjacent to it. Generically, we find that densities and mobilities of both water and dissolved ions are spatially heterogeneous in the plane parallel to the electrode over nanosecond timescales. These and other recent results are analyzed in the context of available experimental literature from surface science and electrochemistry. We speculate on the implications of this emerging microscopic picture on the catalytic proficiency of hydrated electrodes, offering a new direction for study in heterogeneous catalysis at the nanoscale.

Designed electromagnetic pulsed therapy: clinical applications.

PubMed

Gordon, Glen A

2007-09-01

First reduced to science by Maxwell in 1865, electromagnetic technology as therapy received little interest from basic scientists or clinicians until the 1980s. It now promises applications that include mitigation of inflammation (electrochemistry) and stimulation of classes of genes following onset of illness and injury (electrogenomics). The use of electromagnetism to stop inflammation and restore tissue seems a logical phenomenology, that is, stop the inflammation, then upregulate classes of restorative gene loci to initiate healing. Studies in the fields of MRI and NMR have aided the understanding of cell response to low energy EMF inputs via electromagnetically responsive elements. Understanding protein iterations, that is, how they process information to direct energy, we can maximize technology to aid restorative intervention, a promising step forward over current paradigms of therapy.

Complementarity in radiochemical and infrared spectroscopic characterization of electrode adsorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wieckowski, A.

1994-03-01

Radioactive labelling and infrared spectroscopy are frequently used as direct, in situ probes into the structure of the electrochemical solid/liquid interface. These techniques are compared, in a polemical fashion, in the context of a recent publication by Parry et al. (Langmuir 1993, 9, 1878) where the research potential of the former technique was not adequately depicted. It is shown that radiotracers can clearly differentiate between the surface and solution species, both neutrals and anions. In addition to the surface specificity, the radiotracers offer a quantitative determination of adsorbate surface concentrations, a feature not yet demonstrated with surface infrared spectroscopy inmore » electrochemistry. Therefore, these two techniques are complementary. Examples of the combined radiochemical and spectroscopic measurements of adsorption with equivalent (smooth) electrode surfaces are quoted. 11 refs., 2 figs.« less

Direct conversion technology

NASA Technical Reports Server (NTRS)

Massier, Paul F.; Bankston, C. P.; Williams, R.; Underwood, M.; Jeffries-Nakamura, B.; Fabris, G.

1989-01-01

The overall objective of the Direct Conversion Technology task is to develop an experimentally verified technology base for promising direct conversion systems that have potential application for energy conservation in the end-use sectors. This report contains progress of research on the Alkali Metal Thermal-to-Electric Converter (AMTEC), and on the Two-Phase Liquid-Metal Magnetohydrodynamic Electrical Generator (LMMHD) for the period January 1, 1989 through December 31, 1989. Research on these concepts was initiated during October 1987. Reports prepared on previous occasions contain discussions on the following other direct conversion concepts: thermoelectric, pyroelectric, thermionic, thermophotovoltaic, thermoacoustic, thermomagnetic, thermoelastic (nitinol heat engines); and also, more complete discussions of AMTEC and LMMHD systems.

Direct patterning of a cyclotriveratrylene derivative for directed self-assembly of C60

NASA Astrophysics Data System (ADS)

Osner, Zachary R.; Nyamjav, Dorjderem; Holz, Richard C.; Becker, Daniel P.

2011-07-01

A novel apex-modified cyclotriveratrylene (CTV) derivative with an attached thiolane-containing lipoic acid linker was directly patterned onto gold substrates via dip-pen nanolithography (DPN). The addition of a dithiolane-containing linker to the apex of CTV provides a molecule that can adhere to a gold surface with its bowl-shaped cavity directed away from the surface, thereby providing a surface-bound CTV host that can be used for the directed assembly of guest molecules. Subsequent exposure of these CTV microarrays to C60 in toluene resulted in the directed assembly of predesigned, spatially controlled, high-density microarrays of C60. The molecular recognition capabilities of this CTV template toward C60 provides proof-of-concept that supramolecular CTV scaffolds can be directly patterned onto surfaces providing a foundation for the development of organic electronic and optoelectronic materials.

Conception d'un outil d'aide a la decision de technologies de fabrication additive en milieu aeronautique

NASA Astrophysics Data System (ADS)

Buvat, Gael

La fabrication additive offre une opportunite d'amelioration des methodes de productions de pieces. Cependant, les technologies de fabrication additive sont diverses, les fournisseurs de services sont multiples et peu de personnel est forme pour operer sur ces technologies. L'objectif de cette etude est d'emettre une suggestion de concepts d'outils d'aide a la decision de technologies, de materiaux et de post-traitements de fabrication additive en milieu aeronautique. Trois sous-objectifs sont employes. Premierement, la definition des criteres de decision de technologies, de materiaux et de post-traitements de fabrication additive. Ensuite, l'elaboration d'un cahier des charges de l'outil d'aide a la decision en accord avec les besoins industriels du secteur aeronautique. Et enfin, la suggestion de trois concepts d'outils d'aide a la decision et leur evaluation par comparaison au cahier des charges etabli. Les criteres captures aupres de 11 industriels concernent des criteres de couts, de qualite, de conception et de delai d'obtention. Ensuite, nous avons elabore un cahier des charges permettant de reunir les besoins des industriels du secteur aeronautique selon trois axes qui constituent la colonne vertebrale des outils d'aide a la decision : une suggestion d'interface utilisateur, une suggestion de bases de donnees et un moteur de selection des technologies, des materiaux et des post-traitements de fabrication additive. La convivialite de l'interface utilisateur, l'evaluation de la qualite souhaitee par l'utilisateur et la prise en compte des etudes de cas realisees par le moteur de selection sont exemples de besoins que nous avons identifie au sein de cette etude. Nous avons ensuite transcrit ces besoins en specifications techniques pour permettre une evaluation du niveau de satisfaction des industriels au travers d'un pointage des trois concepts suggeres. Ces trois concepts d'outils d'aide a la decision ont ete realises respectivement grâce a Microsoft Excel

Adult-Directed and Peer-Directed Respect for Authority: Relationships With Aggressive and Manipulative Behavior.

PubMed

Clemans, Katherine H; Graber, Julia A; Bettencourt, Amie F

2012-09-01

This study investigated whether respect for adult and peer authority are separate attitudes which have distinct relationships with aggressive and manipulative behavior. Items assessing admiration for and obedience toward parents, teachers, popular students, and friend group leaders were administered to 286 middle school students (M age = 12.6 yrs). Factor analysis revealed two primary factors which corresponded to adult-directed and peer-directed respect orientations. Results suggested that adult-directed respect was associated with lower levels of aggression and social manipulation, whereas peer-directed respect was associated with higher levels of these behaviors. The role of peer-directed respect as a risk factor for negative social behavior in adolescence is discussed.

TUNGSTEN BRONZE RELATED NON-NOBLE ELECTROCATALYSTS.

DTIC Science & Technology

FUEL CELLS, *CATALYSTS), (*OXYGEN, *ELECTRODES), (* SILICIDES , ELECTRODES), (*CARBIDES, ELECTRODES), (*TUNGSTEN COMPOUNDS, *ELECTROCHEMISTRY...CATALYSTS, TITANIUM COMPOUNDS, ZIRCONIUM COMPOUNDS, VANADIUM COMPOUNDS, NIOBIUM COMPOUNDS, TUNGSTEN COMPOUNDS, TANTALUM COMPOUNDS, MOLYBDENUM COMPOUNDS, SULFURIC ACID, CRYSTAL GROWTH, SODIUM COMPOUNDS

Wet Labs, Computers, and Spreadsheets.

ERIC Educational Resources Information Center

Durham, Bill

1990-01-01

Described are some commonly encountered chemistry experiments that have been modified for computerized data acquisition. Included are exercises in radioactivity, titration, calorimetry, kinetics, and electrochemistry. Software considerations and laboratory procedures are discussed. (CW)

Dark matter spin determination with directional direct detection experiments

NASA Astrophysics Data System (ADS)

Catena, Riccardo; Conrad, Jan; Döring, Christian; Ferella, Alfredo Davide; Krauss, Martin B.

2018-01-01

If dark matter has spin 0, only two WIMP-nucleon interaction operators can arise as leading operators from the nonrelativistic reduction of renormalizable single-mediator models for dark matter-quark interactions. Based on this crucial observation, we show that about 100 signal events at next generation directional detection experiments can be enough to enable a 2 σ rejection of the spin 0 dark matter hypothesis in favor of alternative hypotheses where the dark matter particle has spin 1 /2 or 1. In this context, directional sensitivity is crucial since anisotropy patterns in the sphere of nuclear recoil directions depend on the spin of the dark matter particle. For comparison, about 100 signal events are expected in a CF4 detector operating at a pressure of 30 torr with an exposure of approximately 26,000 cubic-meter-detector days for WIMPs of 100 GeV mass and a WIMP-fluorine scattering cross section of 0.25 pb. Comparable exposures require an array of cubic meter time projection chamber detectors.

Directionality of real world networks as predicted by path length in directed and undirected graphs

NASA Astrophysics Data System (ADS)

Rosen, Yonatan; Louzoun, Yoram

2014-05-01

Many real world networks either support ordered processes, or are actually representations of such processes. However, the same networks contain large strong connectivity components and long circles, which hide a possible inherent order, since each vertex can be reached from each vertex in a directed path. Thus, the presence of an inherent directionality in networks may be hidden. We here discuss a possible definition of such a directionality and propose a method to detect it. Several common algorithms, such as the betweenness centrality or the degree, measure various aspects of centrality in networks. However, they do not address directly the issue of inherent directionality. The goal of the algorithm discussed here is the detection of global directionality in directed networks. Such an algorithm is essential to detangle complex networks into ordered process. We show that indeed the vast majority of measured real world networks have a clear directionality. Moreover, this directionality can be used to classify vertices in these networks from sources to sinks. Such an algorithm can be highly useful in order to extract a meaning from large interaction networks assembled in many domains.

Flight directions of passerine migrants in daylight and darkness: A radar and direct visual study

NASA Technical Reports Server (NTRS)

Gauthreaux, S. A., Jr.

1972-01-01

The application of radar and visual techniques to determine the migratory habits of passerine birds during daylight and darkness is discussed. The effects of wind on the direction of migration are examined. Scatter diagrams of daytime and nocturnal migration track directions correlated with wind direction are presented. It is concluded that migratory birds will fly at altitudes where wind direction and migratory direction are nearly the same. The effects of cloud cover and solar obscuration are considered negligible.

French payload specialist Patrick Baudry prepares a meal

NASA Image and Video Library

1985-06-17

51G-08-021 (17-24 June 1985) --- Patrick Baudry, payload specialist representing the Centre National d'Etudes Spatiales of France, prepares to open a can of lobster. The bag attached to a nearby locker door appears to contain several other French snacks.

A New Approach to Electrical Characterization of Exploding Foil Initiators

DTIC Science & Technology

1998-12-01

processed to illustrate the methodology. RESUME Dans une etude precedente de 1a caracterisation electrique des detonateurs a element projete (DEP), on a...applicable a 1a caracterisation electrique des DEP et decrit la methodologie experimentale adequate. Cette methodologie est illustree par la

French research program on the physiological problems caused by weightlessness. Use of the primate model

NASA Astrophysics Data System (ADS)

Pesquies, P. C.; Milhaud, C.; Nogues, C.; Klein, M.; Cailler, B.; Bost, R.

The need to acquire a better knowledge of the main biological problems induced by microgravity implies—in addition to human experimentation—the use of animal models, and primates seem to be particularly well adapted to this type of research. The major areas of investigation to be considered are the phospho-calcium metabolism and the metabolism of supporting tissues, the hydroelectrolytic metabolism, the cardiovascular function, awakeness, sleep-awakeness cycles, the physiology of equilibrium and the pathophysiology of space sickness. Considering this program, the Centre d'Etudes et de Recherches de Medecine Aerospatiale, under the sponsorship of the Centre National d'Etudes Spatiales, developed both a program of research on restrained primates for the French-U.S. space cooperation (Spacelab program) and for the French-Soviet space cooperation (Bio-cosmos program), and simulation of the effects of microgravity by head-down bedrest. Its major characteristics are discussed in the study.

Fractal dimension analysis of complexity in Ligeti piano pieces

NASA Astrophysics Data System (ADS)

Bader, Rolf

2005-04-01

Fractal correlation dimensional analysis has been performed with whole solo piano pieces by Gyrgy Ligeti at every 50ms interval of the pieces. The resulting curves of development of complexity represented by the fractal dimension showed up a very reasonable correlation with the perceptional density of events during these pieces. The seventh piece of Ligeti's ``Musica ricercata'' was used as a test case. Here, each new part of the piece was followed by an increase of the fractal dimension because of the increase of information at the part changes. The second piece ``Galamb borong,'' number seven of the piano Etudes was used, because Ligeti wrote these Etudes after studying fractal geometry. Although the piece is not fractal in the strict mathematical sense, the overall structure of the psychoacoustic event-density as well as the detailed event development is represented by the fractal dimension plot.

Adult-Directed and Peer-Directed Respect for Authority: Relationships With Aggressive and Manipulative Behavior

PubMed Central

Clemans, Katherine H.; Graber, Julia A.; Bettencourt, Amie F.

2012-01-01

This study investigated whether respect for adult and peer authority are separate attitudes which have distinct relationships with aggressive and manipulative behavior. Items assessing admiration for and obedience toward parents, teachers, popular students, and friend group leaders were administered to 286 middle school students (M age = 12.6 yrs). Factor analysis revealed two primary factors which corresponded to adult-directed and peer-directed respect orientations. Results suggested that adult-directed respect was associated with lower levels of aggression and social manipulation, whereas peer-directed respect was associated with higher levels of these behaviors. The role of peer-directed respect as a risk factor for negative social behavior in adolescence is discussed. PMID:23329877

Direct deposit of catalyst on the membrane of direct feed fuel cells

NASA Technical Reports Server (NTRS)

Chun, William (Inventor); Narayanan, Sekharipuram R. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor); Linke, Juergen (Inventor)

2001-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Catalyst utilization and catalyst/membrane interface improvements are disclosed. Specifically, the catalyst layer is applied directly onto the membrane electrolyte.

Electropolymerized Conducting Polymer as Actuator and Sensor Device

ERIC Educational Resources Information Center

Cortes, Maria T.; Moreno, Juan C.

2005-01-01

A study demonstrates the potential application of conducting polymers to convert electrical energy into mechanical energy at low voltage or current. The performance of the device is explained using electrochemistry and solid-state chemistry.

Modular Approach to Instrumental Analysis.

ERIC Educational Resources Information Center

Deming, Richard L.; And Others

1982-01-01

To remedy certain deficiencies, an instrument analysis course was reorganized into six one-unit modules: optical spectroscopy, magnetic resonance, separations, electrochemistry, radiochemistry, and computers and interfacing. Selected aspects of the course are discussed. (SK)

Applications of Payload Directed Flight

NASA Technical Reports Server (NTRS)

Ippolito, Corey; Fladeland, Matthew M.; Yeh, Yoo Hsiu

2009-01-01

Next generation aviation flight control concepts require autonomous and intelligent control system architectures that close control loops directly around payload sensors in manner more integrated and cohesive that in traditional autopilot designs. Research into payload directed flight control at NASA Ames Research Center is investigating new and novel architectures that can satisfy the requirements for next generation control and automation concepts for aviation. Tighter integration between sensor and machine requires definition of specific sensor-directed control modes to tie the sensor data directly into a vehicle control structures throughout the entire control architecture, from low-level stability- and control loops, to higher level mission planning and scheduling reasoning systems. Payload directed flight systems can thus provide guidance, navigation, and control for vehicle platforms hosting a suite of onboard payload sensors. This paper outlines related research into the field of payload directed flight; and outlines requirements and operating concepts for payload directed flight systems based on identified needs from the scientific literature.'

Direct work function measurement by gas phase photoelectron spectroscopy and its application on PbS nanoparticles.

PubMed

Axnanda, Stephanus; Scheele, Marcus; Crumlin, Ethan; Mao, Baohua; Chang, Rui; Rani, Sana; Faiz, Mohamed; Wang, Suidong; Alivisatos, A Paul; Liu, Zhi

2013-01-01

Work function is a fundamental property of a material's surface. It is playing an ever more important role in engineering new energy materials and efficient energy devices, especially in the field of photovoltaic devices, catalysis, semiconductor heterojunctions, nanotechnology, and electrochemistry. Using ambient pressure X-ray photoelectron spectroscopy (APXPS), we have measured the binding energies of core level photoelectrons of Ar gas in the vicinity of several reference materials with known work functions (Au(111), Pt(111), graphite) and PbS nanoparticles. We demonstrate an unambiguously negative correlation between the work functions of reference samples and the binding energies of Ar 2p core level photoelectrons detected from the Ar gas near the sample surface region. Using this experimentally determined linear relationship between the surface work function and Ar gas core level photoelectron binding energy, we can measure the surface work function of different materials under different gas environments. To demonstrate the potential applications of this ambient pressure XPS technique in nanotechnology and solar energy research, we investigate the work functions of PbS nanoparticles with various capping ligands: methoxide, mercaptopropionic acid, and ethanedithiol. Significant Fermi level position changes are observed for PbS nanoparticles when the nanoparticle size and capping ligands are varied. The corresponding changes in the valence band maximum illustrate that an efficient quantum dot solar cell design has to take into account the electrochemical effect of the capping ligand as well.

Consistency between direct and indirect trial evidence: is direct evidence always more reliable?

PubMed

Madan, Jason; Stevenson, Matt D; Cooper, Katy L; Ades, A E; Whyte, Sophie; Akehurst, Ron

2011-01-01

To present a case study involving the reduction in incidence of febrile neutropenia (FN) after chemotherapy with granulocyte colony-stimulating factors (G-CSFs), illustrating difficulties that may arise when following the common preference for direct evidence over indirect evidence. Evidence of the efficacy of treatments was identified from two previous systematic reviews. We used Bayesian evidence synthesis to estimate relative treatment effects based on direct evidence, indirect evidence, and both pooled together. We checked for inconsistency between direct and indirect evidence and explored the role of one specific trial using cross-validation. A subsequent review identified further studies not available at the time of the original analysis. We repeated the analyses on the enlarged evidence base. We found substantial inconsistency in the original evidence base. The median odds ratio of FN for primary pegfilgrastim versus no primary G-CSF was 0.06 (95% credible interval: 0.02-0.19) based on direct evidence, but 0.27 (95% credible interval: 0.13-0.53) based on indirect evidence (P value for consistency hypothesis 0.027). The additional trials were consistent with the earlier indirect, rather than the direct, evidence, and there was no inconsistency between direct and indirect estimates in the updated evidence. The earlier inconsistency was due to one trial comparing primary pegfilgrastim with no primary G-CSF. Predictive cross-validation showed that this study was inconsistent with the evidence as a whole and with other trials making this comparison. Both the Cochrane Handbook and the NICE Methods Guide express a preference for direct evidence. A more robust strategy, which is in line with the accepted principles of evidence synthesis, would be to combine all relevant and appropriate information, whether direct or indirect. Copyright © 2011 International Society for Pharmacoeconomics and Outcomes Research (ISPOR). Published by Elsevier Inc. All rights reserved.

Materials research at Stanford University

NASA Technical Reports Server (NTRS)

1976-01-01

Information briefly describing the total research activity related to the science of materials is reported. Emphasis is placed on physical and mechanical properties of composite materials, energy transportation, superconductors, microwave electronics, and solid state electrochemistry.

Phoenix Wet Chemistry Laboratory Units

NASA Image and Video Library

2008-06-26

This image shows four Wet Chemistry Laboratory units, part of the Microscopy, Electrochemistry, and Conductivity Analyzer MECA instrument on board NASA Phoenix Mars Lander. This image was taken before Phoenix launch on August 4, 2007.

On Comparing Precision Orbit Solutions of Geodetic Satellites Given Several Atmospheric Density Models

DTIC Science & Technology

2014-08-01

Astrodynamics, drag, atmospheric density, geodesy 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT UU 18. NUMBER OF PAGES 12 19a...Translation of ’Le satellite de geodesie ’Starlette’,’ Groupe de Recherches de Geodesie Spatiale, Centre National d’Etudes Spatiales, Bretigny-sur-Orge

Homeland Security Presidential Directives

EPA Pesticide Factsheets

Three of these directives directly affect EPA's role in the national emergency response system: HSPD-5 Management of Domestic Incidents; HSPD-7 Critical Infrastructure Identification, Prioritization, and Protection; and HSPD-8 National Preparedness.

How directional change in reading/writing habits relates to directional change in displayed pictures.

PubMed

Lee, Hachoung; Oh, Songjoo

2016-01-01

It has been suggested that reading/writing habits may influence the appreciation of pictures. For example, people who read and write in a rightward direction have an aesthetic preference for pictures that face rightward over pictures that face leftward, and vice versa. However, correlations for this phenomenon have only been found in cross-cultural studies. Will a directional change in reading/writing habits within a culture relate to changes in picture preference? Korea is a good place to research this question because the country underwent gradual changes in reading/writing direction habits, from leftward to rightward, during the 20th century. In this study, we analyzed the direction of drawings and photos published in the two oldest newspapers in Korea from 1920-2013. The results show that the direction of the drawings underwent a clear shift from the left to the right, but the direction of the photos did not change. This finding suggests a close psychological link between the habits of reading/writing and drawing that cannot be accounted for simply by an accidental correspondence across different cultures.

Visual direction finding by fishes

NASA Technical Reports Server (NTRS)

Waterman, T. H.

1972-01-01

The use of visual orientation, in the absence of landmarks, for underwater direction finding exercises by fishes is reviewed. Celestial directional clues observed directly near the water surface or indirectly at an asymptatic depth are suggested as possible orientation aids.

Assessment of Battery Technology for Rail Propulsion Application

DOT National Transportation Integrated Search

2017-08-01

The study's authors conducted a review of various battery chemistries, including information on basic electrochemistry and the critical parameters that drive battery design and sizing. The authors examined the performance, life cycle, and safety of l...

Science Notes.

ERIC Educational Resources Information Center

School Science Review, 1990

1990-01-01

Included are 30 science activities that include computer monitoring, fieldwork, enzyme activity, pH, drugs, calorimeters, Raoult's Law, food content, solubility, electrochemistry, titration, physical properties of materials, gel filtration, energy, concepts in physics, and electricity. (KR)

Operando observations of solid-state electrochemical reactions in Li-ion batteries by spatially resolved TEM EELS and electron holography.

PubMed

Yamamoto, Kazuo; Iriyama, Yasutoshi; Hirayama, Tsukasa

2017-02-08

All-solid-state Li-ion batteries having incombustible solid electrolytes are promising energy storage devices because they have significant advantages in terms of safety, lifetime and energy density. Electrochemical reactions, namely, Li-ion insertion/extraction reactions, commonly occur around the nanometer-scale interfaces between the electrodes and solid electrolytes. Thus, transmission electron microscopy (TEM) is an appropriate technique to directly observe such reactions, providing important information for understanding the fundamental solid-state electrochemistry and improving battery performance. In this review, we introduce two types of TEM techniques for operando observations of battery reactions, spatially resolved electron energy-loss spectroscopy in a TEM mode for direct detection of the Li concentration profiles and electron holography for observing the electric potential changes due to Li-ion insertion/extraction reactions. We visually show how Li-ion insertion/extractions affect the crystal structures, electronic structures, and local electric potential during the charge-discharge processes in these batteries. © The Author 2016. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

A photoacoustic imaging reconstruction method based on directional total variation with adaptive directivity.

PubMed

Wang, Jin; Zhang, Chen; Wang, Yuanyuan

2017-05-30

In photoacoustic tomography (PAT), total variation (TV) based iteration algorithm is reported to have a good performance in PAT image reconstruction. However, classical TV based algorithm fails to preserve the edges and texture details of the image because it is not sensitive to the direction of the image. Therefore, it is of great significance to develop a new PAT reconstruction algorithm to effectively solve the drawback of TV. In this paper, a directional total variation with adaptive directivity (DDTV) model-based PAT image reconstruction algorithm, which weightedly sums the image gradients based on the spatially varying directivity pattern of the image is proposed to overcome the shortcomings of TV. The orientation field of the image is adaptively estimated through a gradient-based approach. The image gradients are weighted at every pixel based on both its anisotropic direction and another parameter, which evaluates the estimated orientation field reliability. An efficient algorithm is derived to solve the iteration problem associated with DDTV and possessing directivity of the image adaptively updated for each iteration step. Several texture images with various directivity patterns are chosen as the phantoms for the numerical simulations. The 180-, 90- and 30-view circular scans are conducted. Results obtained show that the DDTV-based PAT reconstructed algorithm outperforms the filtered back-projection method (FBP) and TV algorithms in the quality of reconstructed images with the peak signal-to-noise rations (PSNR) exceeding those of TV and FBP by about 10 and 18 dB, respectively, for all cases. The Shepp-Logan phantom is studied with further discussion of multimode scanning, convergence speed, robustness and universality aspects. In-vitro experiments are performed for both the sparse-view circular scanning and linear scanning. The results further prove the effectiveness of the DDTV, which shows better results than that of the TV with sharper image edges and

75 FR 57217 - Direct Investment Surveys: BE-11, Annual Survey of U.S. Direct Investment Abroad

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-20

...] RIN 0691-AA74 Direct Investment Surveys: BE-11, Annual Survey of U.S. Direct Investment Abroad AGENCY... the reporting requirements for the BE-11, Annual Survey of U.S. Direct Investment Abroad. The survey.... Direct Investment Abroad. These amendments include changes in form design and reporting thresholds, as...

Epidemic threshold in directed networks.

PubMed

Li, Cong; Wang, Huijuan; Van Mieghem, Piet

2013-12-01

Epidemics have so far been mostly studied in undirected networks. However, many real-world networks, such as the online social network Twitter and the world wide web, on which information, emotion, or malware spreads, are directed networks, composed of both unidirectional links and bidirectional links. We define the directionality ξ as the percentage of unidirectional links. The epidemic threshold τ(c) for the susceptible-infected-susceptible (SIS) epidemic is lower bounded by 1/λ(1) in directed networks, where λ(1), also called the spectral radius, is the largest eigenvalue of the adjacency matrix. In this work, we propose two algorithms to generate directed networks with a given directionality ξ. The effect of ξ on the spectral radius λ(1), principal eigenvector x(1), spectral gap (λ(1)-|λ(2)|), and algebraic connectivity μ(N-1) is studied. Important findings are that the spectral radius λ(1) decreases with the directionality ξ, whereas the spectral gap and the algebraic connectivity increase with the directionality ξ. The extent of the decrease of the spectral radius depends on both the degree distribution and the degree-degree correlation ρ(D). Hence, in directed networks, the epidemic threshold is larger and a random walk converges to its steady state faster than that in undirected networks with the same degree distribution.

Epidemic threshold in directed networks

NASA Astrophysics Data System (ADS)

Li, Cong; Wang, Huijuan; Van Mieghem, Piet

2013-12-01

Epidemics have so far been mostly studied in undirected networks. However, many real-world networks, such as the online social network Twitter and the world wide web, on which information, emotion, or malware spreads, are directed networks, composed of both unidirectional links and bidirectional links. We define the directionality ξ as the percentage of unidirectional links. The epidemic threshold τc for the susceptible-infected-susceptible (SIS) epidemic is lower bounded by 1/λ1 in directed networks, where λ1, also called the spectral radius, is the largest eigenvalue of the adjacency matrix. In this work, we propose two algorithms to generate directed networks with a given directionality ξ. The effect of ξ on the spectral radius λ1, principal eigenvector x1, spectral gap (λ1-λ2), and algebraic connectivity μN-1 is studied. Important findings are that the spectral radius λ1 decreases with the directionality ξ, whereas the spectral gap and the algebraic connectivity increase with the directionality ξ. The extent of the decrease of the spectral radius depends on both the degree distribution and the degree-degree correlation ρD. Hence, in directed networks, the epidemic threshold is larger and a random walk converges to its steady state faster than that in undirected networks with the same degree distribution.

Gestion des ressources hydriques adaptee aux changements climatiques pour la production optimale d'hydroelectricite. Etude de cas: Bassin versant de la riviere Manicouagan

NASA Astrophysics Data System (ADS)

Haguma, Didier

Il est dorenavant etabli que les changements climatiques auront des repercussions sur les ressources en eau. La situation est preoccupante pour le secteur de production d'energie hydroelectrique, car l'eau constitue le moteur pour generer cette forme d'energie. Il sera important d'adapter les regles de gestion et/ou les installations des systemes hydriques, afin de minimiser les impacts negatifs et/ou pour capitaliser sur les retombees positives que les changements climatiques pourront apporter. Les travaux de la presente recherche s'interessent au developpement d'une methode de gestion des systemes hydriques qui tient compte des projections climatiques pour mieux anticiper les impacts de l'evolution du climat sur la production d'hydroelectricite et d'etablir des strategies d'adaptation aux changements climatiques. Le domaine d'etude est le bassin versant de la riviere Manicouagan situe dans la partie centrale du Quebec. Une nouvelle approche d'optimisation des ressources hydriques dans le contexte des changements climatiques est proposee. L'approche traite le probleme de la saisonnalite et de la non-stationnarite du climat d'une maniere explicite pour representer l'incertitude rattachee a un ensemble des projections climatiques. Cette approche permet d'integrer les projections climatiques dans le probleme d'optimisation des ressources en eau pour une gestion a long terme des systemes hydriques et de developper des strategies d'adaptation de ces systemes aux changements climatiques. Les resultats montrent que les impacts des changements climatiques sur le regime hydrologique du bassin de la riviere Manicouagan seraient le devancement et l'attenuation de la crue printaniere et l'augmentation du volume annuel d'apports. L'adaptation des regles de gestion du systeme hydrique engendrerait une hausse de la production hydroelectrique. Neanmoins, une perte de la performance des installations existantes du systeme hydrique serait observee a cause de l'augmentation des

Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries

PubMed Central

2017-01-01

The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. This discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond. PMID:28691072

Directing the lithium–sulfur reaction pathway via sparingly solvating electrolytes for high energy density batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Chang -Wook; Pang, Quan; Ha, Seungbum

The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparinglymore » solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. Finally, this discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond.« less

Directing the lithium–sulfur reaction pathway via sparingly solvating electrolytes for high energy density batteries

DOE PAGES

Lee, Chang -Wook; Pang, Quan; Ha, Seungbum; ...

2017-05-25

The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparinglymore » solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. Finally, this discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond.« less

Potential Theory for Directed Networks

PubMed Central

Zhang, Qian-Ming; Lü, Linyuan; Wang, Wen-Qiang; Zhou, Tao

2013-01-01

Uncovering factors underlying the network formation is a long-standing challenge for data mining and network analysis. In particular, the microscopic organizing principles of directed networks are less understood than those of undirected networks. This article proposes a hypothesis named potential theory, which assumes that every directed link corresponds to a decrease of a unit potential and subgraphs with definable potential values for all nodes are preferred. Combining the potential theory with the clustering and homophily mechanisms, it is deduced that the Bi-fan structure consisting of 4 nodes and 4 directed links is the most favored local structure in directed networks. Our hypothesis receives strongly positive supports from extensive experiments on 15 directed networks drawn from disparate fields, as indicated by the most accurate and robust performance of Bi-fan predictor within the link prediction framework. In summary, our main contribution is twofold: (i) We propose a new mechanism for the local organization of directed networks; (ii) We design the corresponding link prediction algorithm, which can not only testify our hypothesis, but also find out direct applications in missing link prediction and friendship recommendation. PMID:23408979

Directional detector of gamma rays

DOEpatents

Cox, Samson A.; Levert, Francis E.

1979-01-01

A directional detector of gamma rays comprises a strip of an electrical cuctor of high atomic number backed with a strip of a second electrical conductor of low atomic number. These elements are enclosed within an electrical conductor that establishes an electrical ground, maintains a vacuum enclosure and screens out low-energy gamma rays. The detector exhibits a directional sensitivity marked by an increased output in the favored direction by a factor of ten over the output in the unfavored direction.

75 FR 80294 - Direct Investment Surveys: BE-11, Annual Survey of U.S. Direct Investment Abroad

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-22

...] RIN 0691-AA74 Direct Investment Surveys: BE-11, Annual Survey of U.S. Direct Investment Abroad AGENCY... for the BE-11, Annual Survey of U.S. Direct Investment Abroad. BEA conducts the survey annually and.... Direct Investment Abroad. DATES: This final rule will be effective January 21, 2011. FOR FURTHER...

Bi-directional transition nets

NASA Astrophysics Data System (ADS)

Staines, Anthony Spiteri

2017-06-01

Ordinary Petri nets are forward directed transition systems. Modern transition systems events and event flows are reversible. Hence modeling structures that reflect this are important. The creation of a bi-directional Petri net extends the modeling power of Petri nets. This work presents the successful implementation of a bi-directional transition net. Some toy examples in comparison to Petri nets are given showing the increased modeling power in a compacted form. The results show some interesting findings on how the expressive power of these structures has been increased.

European Organization for Research and Treatment of Cancer and Groupe d'Etude des Lymphomes de l'Adulte very favorable and favorable, lymphocyte-predominant Hodgkin disease.

PubMed

Wilder, Richard B; Schlembach, Pamela J; Jones, Dan; Chronowski, Gregory M; Ha, Chul S; Younes, Anas; Hagemeister, Fredrick B; Barista, Ibrahim; Cabanillas, Fernando; Cox, James D

2002-03-15

Lymphocyte-predominant Hodgkin disease (LPHD) is rare and has a natural history different from that of classic Hodgkin disease. There is little information in the literature regarding the role of chemotherapy in patients with early-stage LPHD. The objective of this study was to examine recurrence free survival (RFS), overall survival (OS), and patterns of first recurrence in patients with LPHD who were treated with radiotherapy alone or with chemotherapy followed by radiotherapy. From 1963 to 1996, 48 consecutive patients ages 16-49 years (median, 28 years) with Ann Arbor Stage I (n = 30 patients) or Stage II (n = 18 patients), very favorable (VF; n = 5 patients) or favorable (F; n = 43 patients) LPHD, according to the European Organization for Research and Treatment of Cancer and Groupe d'Etude des Lymphomes de l'Adulte (EORTC-GELA) criteria, received radiotherapy alone (n = 37 patients) or received chemotherapy followed by radiotherapy (n = 11 patients). The percentages of patients with VF disease (11% vs. 9% in the radiotherapy group vs. the chemotherapy plus radiotherapy group, respectively) or F disease (89% vs. 91%, respectively) within the two treatment groups were similar (P = 1.00). A median of three cycles of chemotherapy with mechlorethamine, vincristine, procarbazine, and prednisone (MOPP) or with mitoxantrone, vincristine, vinblastine, and prednisone (NOVP) was given initially to six patients and five patients, respectively. A median total radiotherapy dose of 40 grays (Gy) given in daily fractions of 2.0 Gy was delivered to both treatment groups. The median follow-up was 9.3 years, and 98% of patients were observed for > or = 3.0 years. RFS was similar for patients who were treated with radiotherapy alone and patients who were treated with chemotherapy followed by radiotherapy (10-year survival rates: 77% and 68%, respectively; P = 0.89). The OS rate also was similar for the two groups (10-year survival rates: 90% and 100%, respectively; P = 0

Modeling the directivity of parametric loudspeaker

NASA Astrophysics Data System (ADS)

Shi, Chuang; Gan, Woon-Seng

2012-09-01

The emerging applications of the parametric loudspeaker, such as 3D audio, demands accurate directivity control at the audible frequency (i.e. the difference frequency). Though the delay-and-sum beamforming has been proven adequate to adjust the steering angles of the parametric loudspeaker, accurate prediction of the mainlobe and sidelobes remains a challenging problem. It is mainly because of the approximations that are used to derive the directivity of the difference frequency from the directivity of the primary frequency, and the mismatches between the theoretical directivity and the measured directivity caused by system errors incurred at different stages of the implementation. In this paper, we propose a directivity model of the parametric loudspeaker. The directivity model consists of two tuning vectors corresponding to the spacing error and the weight error for the primary frequency. The directivity model adopts a modified form of the product directivity principle for the difference frequency to further improve the modeling accuracy.

Determining wave direction using curvature parameters.

PubMed

de Queiroz, Eduardo Vitarelli; de Carvalho, João Luiz Baptista

2016-01-01

The curvature of the sea wave was tested as a parameter for estimating wave direction in the search for better results in estimates of wave direction in shallow waters, where waves of different sizes, frequencies and directions intersect and it is difficult to characterize. We used numerical simulations of the sea surface to determine wave direction calculated from the curvature of the waves. Using 1000 numerical simulations, the statistical variability of the wave direction was determined. The results showed good performance by the curvature parameter for estimating wave direction. Accuracy in the estimates was improved by including wave slope parameters in addition to curvature. The results indicate that the curvature is a promising technique to estimate wave directions.•In this study, the accuracy and precision of curvature parameters to measure wave direction are analyzed using a model simulation that generates 1000 wave records with directional resolution.•The model allows the simultaneous simulation of time-series wave properties such as sea surface elevation, slope and curvature and they were used to analyze the variability of estimated directions.•The simultaneous acquisition of slope and curvature parameters can contribute to estimates wave direction, thus increasing accuracy and precision of results.

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

Organic Electrochemistry in Aluminum Chloride Melts.

DTIC Science & Technology

1976-08-15

establishing a new, room temperature molten salt system. The low temperature fused salt was prepared by combining aluminum...narrow (600 mY) potential range. Organic electrosynthesis was conducted in a 50-50 by volume molten salt - benzene solution. This mixed solvent...room temperature molten salt system, namely a 67:33 mole percent aluminum chloride: ethylpyridinium bromide melt and in a 50-50 by volume solution of the

Electrochemistry in an acoustically levitated drop.

PubMed

Chainani, Edward T; Ngo, Khanh T; Scheeline, Alexander

2013-02-19

Levitated drops show potential as microreactors, especially when radicals are present as reactants or products. Solid/liquid interfaces are absent or minimized, avoiding adsorption and interfacial reaction of conventional microfluidics. We report amperometric detection in an acoustically levitated drop with simultaneous ballistic addition of reactant. A gold microelectrode sensor was fabricated with a lithographic process; active electrode area was defined by a photosensitive polyimide mask. The microdisk gold working electrode of radius 19 μm was characterized using ferrocenemethanol in aqueous buffer. Using cyclic voltammetry, the electrochemically active surface area was estimated by combining a recessed microdisk electrode model with the Randles-Sevcik equation. Computer-controlled ballistic introduction of reactant droplets into the levitated drop was developed. Chronoamperometric measurements of ferrocyanide added ballistically demonstrate electrochemical monitoring using the microfabricated electrode in a levitated drop. Although concentration increases with time due to drop evaporation, the extent of concentration is predictable with a linear evaporation model. Comparison of diffusion-limited currents in pendant and levitated drops show that convection arising from acoustic levitation causes an enhancement of diffusion-limited current on the order of 16%.

Electrochemistry in ethanol. I. Reference electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zara, A.J.; de S. Bulhoes, L.O.

1982-01-01

The silver/silver nitrate electrode was found to be a suitable reference electrode in ethanolic solutions (2% v/v in water). The concentration of Ag/sup +/ inside the reference electrode is satisfactory in teh 0.1 to 10 mM concentration range. The liquid junction potential is minimized with sufficient supporting electrolyte (e.g., 0.1 to 0.5 M sodium perchlorate). The electrode is suitable for use as reference electrode in potentiometry and in polarography. Preparation is uncomplicated and the product is stable. 4 figures.